The present invention relates to quaternary ammonium compounds and formulations thereof useful as, for instance, paper debonders, fabric softeners, hair conditioners, skin conditioners, paper deinking and ink floatation agents, asphalt emulsion agents, corrosion inhibitor agents, ore floatation agents, pesticide emulsion agents, car drying aid sprays, drilling fluid additives, and the like.
Heretofore quaternary ammonium compounds and a very few dialkyl ammonium compounds (xe2x80x9cconventional quatsxe2x80x9d) have found widespread use in many applications. A variety of conventional quats have been proposed for many uses, for example, in fabric softeners for home use or for industrial and institutional use such as paper debonding. In general, such compounds exhibit properties which present some difficulty in the manufacture, formulation use, aesthetic properties, biodegradability, and environmental compatibility of these compositions. Thus, many of the conventional compositions used for these functions, even if completely biodegradable with time, do not biodegrade as rapidly as could be desired and are thus not considered readily biodegradable. In addition, several of the commercial readily biodegradable softeners, conditioners, and debonders do not function as effectively as the conventional products that are less biodegradable. Thus, to maintain effective levels of performance, increased amounts of such less effective, more readily biodegradable products (such as softeners) must be employed and, as will be readily apparent, this factor decreases the cost-effectiveness of the product.
In addition, the color and the odor of the products using conventional quats also pose problems with many biodegradable raw materials. Color stability and low odor are essential to obtaining customer acceptance and to achieving stable and acceptable long-term product aesthetic properties. Such properties are difficult to achieve with conventional quats. Moreover. there is increasing interest in obtaining fabric softener and personal care formulations which are clear (translucent or transparent) liquids, even to the point of obtaining a crystal-clear dispersion when the formulation is dispensed and dispersed into rinse water (even at levels of 50-100 ppm actives in water). Clear formulations may also offer several performance advantages, depending on the application, for example, clear fabric softeners offer reduced staining of the fabric, improved dispersibility, and greatly improved rewetting of the fabric or other substrate. Discovery of such clear compositions requires careful identification of proper quaternary and/or polyquaternary ammonium compounds, together with appropriate additives, such as solvents and cosolvents, which act together to achieve the desired appearance. The relatively poor solubility of conventional quats also contributes to certain difficulties that will vary, depending on the application. For example, when such conventional quats are used in fabric softeners, their poor solubility inhibits the dispersibility of the fabric softener actives into water and the dispersibility of the formulated fabric softener product into the washing machine.
Yamamura et al., Kokai No. 4[1990]50,375 (Application No. 2[1990] 156,249), relates to a fabric softener composition for laundered fabric containing monoalkoxylated alkylamine acid salts, wherein the term xe2x80x9cmonoalkoxylatedxe2x80x9d means that the compound does not contain any polymeric chains of alkoxy groups (that is, two or more alkoxy groups attached together). The monoalkoxylated alkylamine acids salts of Yamamura et al. are provided in a fabric softener composition wherein the monoalkoxylated alkylamine acid salts comprise between 2 wt. % and 24 wt. % of the composition. Yamamura et al. differs from the instant invention in that the compositions of Yamamura et al. only contain monoalkoxylated derivatives of their alkylamine acids salts, while the instant invention includes polyalkoxylated derivatives of the compounds of the instant invention, wherein the term xe2x80x9cpolyalkoxylatedxe2x80x9d means that the compound contains at least one polymeric chain of alkoxy groups (that is, two or more alkoxy groups attached directly together). Furthermore, Yamamura et al. differs from the instant invention in that the compositions of Yamamura et al. only provide acid salts of their monoalkoxylated alkylamine component, while the instant invention comprises free amines, salts, and quaternized derivatives of the compounds of the instant invention. Moreover, Yamamura et al. differs from the instant invention in that the compositions of Yamamura et al. only provide the monoalkoxylated alkylamine acid salts as a component of a composition that comprises between 2 wt. % and 24 wt. % of the composition and only in combination with other specified ingredients, while the instant invention provides that the compounds of the instant invention can be used alone or in a composition wherein the compounds of the instant invention comprise from 25 wt. % to 100 wt. % of the composition. Lastly, Yamamura et al. differs from the instant invention in that the compositions of Yamamura et al. only are taught for use as a fabric softener composition for laundered fabric, whereas the instant invention provides that the compounds of the instant invention can be used alone or in combination with other components for a variety of other uses, including paper debonding.
Boronat et al., European Patent Application Publication No. 0 525 271 B1, relates to ether amine ester compounds, their quaternary derivatives, and a process for making such compounds. The structure of the ether amine ester compounds of Boronat et al. are distinct from the compounds of the instant invention.
Phan et al., U.S. Pat. No. 5,698,076, (xe2x80x9cPhan et al. (""076)xe2x80x9d) relates to a quaternary ester amine compound and paper web comprising such compounds. The structure of the quaternary ester amine compounds of Phan et al. (""076) are distinct from the compounds of the instant invention, in particular, because they do not contain alkoxylate groups.
Phan et al., U.S. Pat. No. 5,415,737, (xe2x80x9cPhan et al. (""737)xe2x80x9d) relates to a quaternary ester amine compound and paper web comprising such compounds. The structure of the quaternary ester amine compounds of Phan et al. (""737) are distinct from the compounds of the instant invention.
Phan et al., U.S. Pat. No. 5,405,501, (xe2x80x9cPhan et al. (""501)xe2x80x9d) relates to a quaternary ester amine compound and paper web comprising such compounds. The structure of the quaternary amine compounds of Phan et al. (""501) are distinct from the compounds of the instant invention, in particular, because the disclosed prior art compounds do not contain alkoxylate groups.
Phan et al., U.S. Pat. No. 5,279,767, (xe2x80x9cPhan et al. (""767)xe2x80x9d) and Phan et al., U.S. Pat. No. 5,217,576, (xe2x80x9cPhan et al. (""576)xe2x80x9d) each relate to a quaternary ester amine compound and paper web comprising such compounds. The structure of the quaternary amine compounds of Phan et al. (""767) and Phan et al. (""576) are distinct from the compounds of the instant invention, in particular, because the disclosed prior art compounds do not contain alkoxylate groups.
Phan et al., U.S. Pat. No. 5,264,082, (xe2x80x9cPhan et al. (""082)xe2x80x9d) relates to a quaternary ester amine compound and paper web comprising such compounds. The structure of the quaternary ester amine compounds of Phan et al. (""082) are distinct from the compounds of the instant invention.
Phan et al., U.S. Pat. No. 5,262,007, (xe2x80x9cPhan et al. (""007)xe2x80x9d) relates to quaternary ester amine compounds and paper web comprising such compounds. The structure of the quaternary ester amine compounds of Phan et al. (""007) are distinct from the compounds of the instant invention.
Vinson et al., U.S. Pat. No. 5,487,813, relates to a quaternary ester amine compound and a paper web comprising such compounds and carboxymethyl cellulose and cationic starch.
Certain ester quaternary compounds, for example, 2-[(2-hydroxyethyl)octadecylamino]ethyl stearate (CAS Registry Number 52497-24-2), (octadecylimino)diethylene distearate (CAS Registry Number 94945-28-5), and octadecyl bis(hydroxyethyl)amine have been previously used as antistatic and/or antifogging additives for plastics, in particular, for food packaging materials in accordance with 21 C.F.R. xc2xa7178.3130.
Thus, there remains a need for identification of new amine and ammonium derivatives which are useful as fabric softeners and paper debonders and which are also biodegradable, highly effective in softening, debonding, conditioning, and the like, and yet avoid these problems upon manufacture, formulation and use. It is also desirable for the active agents used in hair and skin conditioners, paper debonding compositions, textile softeners, and the like, to be readily biodegradable and to exhibit a satisfactorily high activity. Conventional products have to date not been able to exhibit both properties to a high degree, thus necessitating acceptance of reduced biodegradability or reduced activity. There is thus still a need for compounds exhibiting levels of activity as conditioners, paper debonders, and so on, as the case may be, which are comparable or superior to conventionally employed actives, such as conventional quats, while also exhibiting ready biodegradability.
As can be appreciated, the chemistry of fabric softeners, paper debonders, hair conditioners, skin conditioners, textile softeners, car wax sprays, and the like is challenging. Each of these applications presents its own complications, because the interactions between the various components of the compositions must be considered in addition to the individual chemistry of each component.
The present invention achieves these objectives and also exhibits the properties and advantages described herein.
One aspect of the present invention comprises compounds of the following structural formula (hereinafter xe2x80x9cstructural formula (IA)xe2x80x9d): 
and the protonated and quaternized derivatives thereof (hereinafter xe2x80x9cstructural formula (1B)xe2x80x9d): 
wherein
R1 is a C2 to C22, preferably C3 to C22, more preferably C4 to C22, even more preferably C5 to C22 or C6 to C22, or C7 to C22, and most preferably C8 to C22, hydrocarbyl group or is an ether group of the formula Rxe2x80x94Oxe2x80x94(F3)vxe2x80x94C3H6xe2x80x94, where v is 0 to 10 and R is a C1 to C22, preferably C4 to C22, hydrocarbyl group;
R2 is hydrogen or a C1 to C22 hydrocarbyl group, or is 
xe2x80x83or (R3)yH, where y is 1 to 100;
each R3 is independently selected from a group consisting of an ethylene oxide group (C2H4O), a propylene oxide group (C3H6O), a butylene oxide group (C4H8O) and mixtures thereof;
each R4 is a C3 to C21, preferably C11 to C21, hydrocarbyl group;
R5 is hydrogen or a C1 to C8 hydrocarbyl group; and
x is 1 to 100; and
A31  is an anion as defined below.
As used herein, the term xe2x80x9calkylxe2x80x9d refers to fully saturated linear (straight-chain) and branched hydrocarbon groups, for example, alkyl includes linear and branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups. As used herein, the term xe2x80x9calkenylxe2x80x9d refers to linear or branched hydrocarbon groups containing at least one carbon-carbon double bond. As used herein, the term xe2x80x9calkynylxe2x80x9d refers to linear or branched hydrocarbon groups containing at least one carbon-carbon triple bond. As used herein, the term xe2x80x9caliphaticxe2x80x9d refers to linear or branched, saturated or unsaturated, hydrocarbon groups, that is, alkyl groups, alkenyl groups, and alkynyl groups. As used herein, the terms xe2x80x9ccycloalkylxe2x80x9d or xe2x80x9ccyclic alkylxe2x80x9d refer to fully saturated hydrocarbon groups containing one, two, three, or more cyclic rings. As used herein, the terms xe2x80x9ccycloalkenylxe2x80x9d or xe2x80x9ccyclic alkenylxe2x80x9d refers to hydrocarbon groups containing one, two, three, or more cyclic rings and at least one double carbon-carbon double bond in the ring, for example, a cyclohexenyl group. As used herein, the term xe2x80x9ccycloaliphaticxe2x80x9d refers herein to saturated or unsaturated hydrocarbon groups containing one, two, three, or more cyclic rings, that is, cycloalkyl groups and cycloalkenyl groups. As used herein, the term xe2x80x9carylxe2x80x9d refers to a group that contains one or more aromatic rings, for example, aryl includes biaryl; biphenylyl; phenyl; naphthyl; phenanthranyl; anthranyl; N-alkyl and N,N-dialkyl anilines; o-, m- and p-nitrophenyl; o-, m- and p-alkyl phenyl; 2-, 3-, and 4-halophenyl; 2-, 3-, and 4-carboxyphenyl and esters thereof; phenol; two aryl groups bridged by an alkylene group; and the substituted derivatives thereof. As used herein, the terms xe2x80x9calkarylxe2x80x9d or xe2x80x9calkylarylxe2x80x9d refer to an alkyl-, alkenyl- or alkynyl-substituted aryl group. As used herein, the terms xe2x80x9caralkylxe2x80x9d or xe2x80x9carylalkylxe2x80x9d refer to an alkyl, alkenyl, or alkynyl group substituted with an aryl group. Examples of aralkyl, include benzyl and substituted benzyl moieties; benzyl halides; benzhydryl halides; trityl halides; a-halo-a-phenylalkanes, such as 1 halo-1-phenylethane, 1-halo-1-phenylpropane, and 1-halo-1-phenyloctadecane; o-, m- and p-chlorobenzyl halides; p-methoxybenzyl halides; o-, m- and p-nitrilobenzyl halides, and o-, m- and p-alkylbenzyl halides. As used herein, the term xe2x80x9chydrocarbylxe2x80x9d refers to aliphatic, cycloaliphatic, aryl, alkaryl, and aralkyl groups. It should be noted that these classifications are not necessarily exclusive for a particular group; thus, a linear aliphatic group containing both a carbon-carbon double bond and a carbon-carbon triple bond may be considered an alkenyl group, an alkynyl group, or both. It is understood that cyclic structures, for example, cycloaliphatic groups and aryl groups, require at least three carbon atoms to form a ring and therefore a term such as xe2x80x9cC1 to C22xe2x80x9d when applied to or modifying such a cyclic structure or applied to a term, for example hydrocarbyl, that includes such cyclic groups, is understood to actually designate only cyclic groups containing 3 to 22 carbon atoms for these cyclic groups.
In preferred embodiments of the invention, the hydrocarbyl groups of R1, R2, R4, and R5 of the compounds of structural formulas (1A) and (1B) are each independently limited to aliphatic, cycloaliphatic, aryl, alkaryl, and aralkyl groups. In other preferred embodiments of the invention, the hydrocarbyl groups of R1, R2, R4, and R5 of the compounds of structural formulas (1A) and (1B) are each independently further limited to alkyl groups, alkenyl groups, and alkynyl groups, each of which may be independently further limited to linear or branched groups; and cycloalkyl groups and cycloalkenyl groups.
In a preferred embodiment of the invention, the compositions and/or formulations of the instant invention comprise compounds of structural formulas (1A) and (1B) which do not contain a significant amount of polymers, plasticizers, polymer stabilizers, or any polymers, plasticizers, or polymer stabilizers. The term xe2x80x9cpolymersxe2x80x9d as used in this paragraph comprises plastics, resins, or polymers known to those of skill in the art that may be selected, without limitation, from the group consisting of natural and synthetic organic polymers, plastics and resins, including aliphatics, polyamides, polyolefins, polypropylenes, polyethylenes, epoxies, polyesters, polycarbonates, polystyrenes, thermoplastics, polyurethanes, polyvinyls, aromatics, nitrogen-containing polymers, synthetic or natural rubbers, phosphorous-containing polymers, or the copolymers, resins, alloys, or blends thereof. The term xe2x80x9cpolymersxe2x80x9d as used in this paragraph does not include the strength additives set forth below in section I. OTHER ADDITIVES, subsection 1. Papermaking and Tissuemaking Additives, subdivision B. Strength Additives.
In a preferred embodiment of the invention, the compositions and/or formulations of the instant invention comprise compounds of structural formulas (1A) and (1B) which do not contain a significant amount of imidazoline compounds, imidazolinium compounds, or imidazoline-derived compounds or any imidazoline compounds, imidazolinium compounds, or imidazoline-derived compounds.
In a preferred embodiment of the invention, the compounds of structural formulas (1A) and (1B) are provided as compositions and/or formulations wherein the compounds of structural formulas (1A) and (1B) comprise 25 wt. % to 100 wt. % of the total composition, more preferably 40 wt. % to 100 wt. % of the total composition, even more preferably 60 wt. % to 100 wt. % of the total composition, and most preferably 75 wt. % to 100 wt. % of the total composition.
In a preferred embodiment of the invention, x is 2 to 50, more preferably x is 3 to 40, even more preferably x is 3 to 30, and most preferably x is 3 to 15. In a preferred embodiment of the invention, R1 is a linear C14 to C22 alkyl or alkylene group, more preferably R1 is a linear Cm,6 to C18 alkyl or alkylene group, and most preferably R1 is selected from the group consisting of stearyl, tall oil fatty acid (TOFA), soya, tallow, canola, and oleyl. In a preferred embodiment of the invention, R2 is a linear or branched C1 to C18 alkyl or alkylene group, more preferably R2 is a linear or branched C12 to C18 alkyl or alkylene group, even more preferably R2 is a linear or branched C14 to Cm,8 alkyl or alkylene group, and most preferably R2 is a linear or branched C16 to C18 alkyl or alkylene group. In yet another preferred embodiment of the invention R2 is 
or (R3)yH, where y is 3 to 50, more preferably y is 3 to 30, and most preferably y is 3 to 15. In a preferred embodiment of the invention, each R4 is independently a linear, branched, or cyclic C13 to C21 alkyl or alkylene group, more preferably each R4 is independently a linear, branched, or cyclic C15 to C21 alkyl or alkylene group, and most preferably each R4 is independently a linear, branched, or cyclic C17 to C21 alkyl or alkylene group. In a preferred embodiment of the invention, R5 is hydrogen, benzyl, or a linear, branched, or cyclic C1 to C6 alkyl or alkylene group, more preferably R5 is hydrogen, benzyl, or a linear or branched C1 to C3 alkyl or alkylene group, and most preferably R5 is hydrogen, methyl, ethyl, or benzyl. In preferred embodiments of the invention, one or more of R1, R2, R4, or R5 does not include any hydroxyl groups. In preferred embodiments of the invention, one or more of R1, R2, R4, or R5 does not include any groups that contain atoms other than hydrogen, carbon, or oxygen.
For home care and personal care products, it is preferred that the compounds of structural formulas (1A) and (1B) contain R1=C8 to C22 hydrocarbyl group or ether wherein R=C4 to C22 hydrocarbyl group and R4=C11 to C21 hydrocarbyl group.
Another aspect of the present invention comprises compounds of the following structural formula (hereinafter xe2x80x9cstructural formula (2A)xe2x80x9d): 
and the protonated and quaternized derivatives thereof (hereinafter xe2x80x9cstructural formula (2B)xe2x80x9d): 
wherein
R1 is a C2 to C22, preferably C3 to C22, more preferably C4 to C22, even more preferably C5 to C22 or C6 to C22, or C7 to C22, and most preferably C8 to C22, hydrocarbyl group or is an ether group of the formula Rxe2x80x94Oxe2x80x94(R3)vxe2x80x94C3H6xe2x80x94, where v is 0 to 10 and R is a C4 to C22 hydrocarbyl
each R2 is independently selected from the group consisting of hydrogen, a C1 to C22 hydrocarbyl group, 
xe2x80x83and (R3)yH, where y is 1 to 100;
each R3 is independently selected from the group consisting of an ethylene oxide group (C2H4O), a propylene oxide group (C3H6O), a butylene oxide group (C4H8O) and mixtures thereof;
each R4 is independently a C3 to C21, preferably C11 to C21,hydrocarbyl group;
each R5 is independently hydrogen or a C1 to C6 hydrocarbyl group, where each w is independently 0 or 1;
each R6 is independently a C1 to C8 hydrocarbyl group;
x is 1 to 100;
z is 1, 2, 3, 4 or 5; and
Axe2x88x92 is an anion as defined below that balances the charge of the compound.
In preferred embodiments of the invention, the hydrocarbyl groups of R1, R2, R4, R5, and R6 of the compounds of structural formulas (2A) and (2B) are each independently limited to aliphatic, cycloaliphatic, aryl, alkaryl, and aralkyl groups. In other preferred embodiments of the invention, the hydrocarbyl groups of R1, R2, R4, R5, and R6 of the compounds of structural formulas (2A) and (2B) are each independently further limited to alkyl groups, alkenyl groups, and alkynyl groups, each of which may be independently further limited to linear or branched groups; and cycloalkyl groups and cycloalkenyl groups.
In a preferred embodiment of the invention, the compositions and/or formulations of the instant invention comprise compounds of structural formulas (2A) and (2B) which do not contain a significant amount of polymers, plasticizers, polymer stabilizers, or any polymers, plasticizers, or polymer stabilizers. The term xe2x80x9cpolymersxe2x80x9d as used in this paragraph comprises plastics, resins, or polymers known to those of skill in the art that may be selected, without limitation, from the group consisting of natural and synthetic organic polymers, plastics and resins, including aliphatics, polyamides, polyolefins, polypropylenes, polyethylenes, epoxies, polyesters, polycarbonates, polystyrenes, thermoplastics, polyurethanes, polyvinyls, aromatics, nitrogen-containing polymers, synthetic or natural rubbers, phosphorous-containing polymers, or the copolymers, resins, alloys, or blends thereof. The term xe2x80x9cpolymersxe2x80x9d as used in this paragraph does not include the strength additives set forth below in section 1. OTHER ADDITIVES, subsection 1. Papermaking and Tissuemaking Additives, subdivision B. Strength Additives.
In a preferred embodiment of the invention, the compositions and/or formulations of the instant invention comprise compounds of structural formulas (2A) and (2B) which do not contain a significant amount of imidazoline compounds, imidazolinium compounds, or imidazoline-derived compounds or any. imidazoline compounds, imidazolinium compounds, or imidazoline-derived compounds.
In a preferred embodiment of the invention, the compounds of structural formulas (2A) and (2B) are provided as compositions and/or formulations wherein the compounds of structural formulas (2A) and (2B) comprise 25 wt. % to 100 wt. % of the total composition, more preferably 40 wt. % to 100 wt. % of the total composition, even more preferably 60 wt. % to 100 wt. % of the total composition, and most preferably 75 wt. % to 100 wt. % of the total composition.
In a preferred embodiment of the invention, x is 2 to 50, more preferably x is 3 to 40, even more preferably x is 3 to 30, and most preferably x is 3 to 15. In a preferred embodiment of the invention, z is 1 or 2, more preferably z is 1. In a preferred embodiment of the invention, R1 is a linear C14 to C22 alkyl or alkylene group, more preferably R1 is a linear C16 to C18 alkyl or alkylene group, and most preferably R1 is selected from the group consisting of stearyl, tall oil fatty acid (TOFA), soya, tallow, canola, and oleyl. In a preferred embodiment of the invention, each R2 is independently a linear or branched C1 to C18 alkyl or alkylene group, more preferably each R2 is independently a linear or branched C12 to C18 alkyl or alkylene group, even more preferably each R2 is independently a linear or branched C14 to C18 alkyl or alkylene group, and most preferably R2 is a linear or branched C16 to C18 alkyl or alkylene group. In yet another preferred embodiment of the invention one or more of R2 is independently a 
or R3)yH, where y is 3 to 50, more preferably y is 3 to 30, and most preferably y is 3 to 15. In a preferred embodiment of the invention, each R4 is independently a linear, branched, or cyclic C13 to C21 alkyl or alkylene group, more preferably each R4 is independently a linear, branched, or cyclic C15 to C21 alkyl or alkylene group, and most preferably each R4 is independently a linear, branched, or cyclic C17 to C21 alkyl or alkylene group. In a preferred embodiment of the invention, R5 is hydrogen, benzyl, or a linear, branched, or cyclic C1 to C6 alkyl or alkylene group, more preferably R5 is hydrogen, benzyl, or a linear or branched C1 to C3 alkyl or alkylene group, and most preferably R5 is hydrogen, methyl, ethyl, or benzyl. In a preferred embodiment of the invention, R6 is a linear, branched, or cyclic C1 to C6 alkyl or alkylene group, more preferably R6 is a linear, branched, or cyclic C3 to C6 alkyl or alkylene group, most preferably R6 is a linear, branched, or cyclic C3 to C5 alkyl or alkylene group containing 3 to 5 carbon atoms. In preferred embodiments of the invention, one or more of R1, R2, R4, R5, or R6 does not include any hydroxyl groups. In preferred embodiments of the invention, one or more of R1, R2, R4, R5, or R6 does not include any groups that contain atoms other than hydrogen, carbon, or oxygen.
In home care and personal care products, it is preferred that compounds of structural formulas (2A) and (2B) contain R1xe2x95x90C8 to C22 hydrocabon or ether wherein Rxe2x95x90C4 to C22 hydrocarbyl group; and R4xe2x95x90C11 to C21 hydrocarbyl group.
As used herein, the term xe2x80x9cstructural formula (1)xe2x80x9d is intended to designate either or both of structural formula (1A) and structural formula (1)B); and the term xe2x80x9cstructural formula (2)xe2x80x9d is intended to designate either of both or structural formula (2A) and structural formula (2B). The compounds of structural formulas (1) and (2), whether in the ester amine form, that is, structural formulas (1A) and (2A), or the protonized species or the quaternized species thereof, that is, structural formulas (1B) and (2B), shall hereinafter be referred to as xe2x80x9cInventive Ester Quatsxe2x80x9d.
If R5 is present, the Inventive Ester Quats are protonized amines or quaternized amines and include an anion Axe2x88x92 which is present in a number of moles equal to the total positive charge of the nitrogen-containing cation thereof (although such may not be explicitly indicated in structural formulas (1)B) and (2B)). The anion Axe2x88x92 can represent any anion which is not deleterious to the properties of the overall compound. Non-limiting examples of Axe2x88x92 include fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, citrate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Preferred examples are chloride, bromide, citrate, acetate, methyl sulfate, ethyl sulfate, and salicylate. If the anion is monovalent (has a charge of xe2x88x921), Axe2x88x92 represents the anion group, if the anion is divalent (has a charge of xe2x88x922), Axe2x88x92 represents half of the anion group, if the anion is trivalent (has a charge of xe2x88x923), Axe2x88x92 represents a third of the anion group, and so on.
The invention also provides a paper web comprising (a) papermaking fibers; and (b) Inventive Ester Quats. In preferred embodiments of the invention, the Inventive Ester Quats comprise from about 0.005% to 5.0% by weight of the papermaking fibers; more preferably from about 0.01% to about 3.0% by weight of the papermaking fibers; even more preferably from about 0.05% to about 2.5% by weight of the papermaking fibers; and most preferably from about 0.1% to about 2.0% by weight of the papermaking fibers.
As used herein, the terms xe2x80x9cpaperxe2x80x9d, xe2x80x9cpaper webxe2x80x9d, xe2x80x9cwebxe2x80x9d, xe2x80x9cpaper sheetxe2x80x9d, xe2x80x9ctissuexe2x80x9d, or xe2x80x9ctissue paperxe2x80x9d is intended to designate an of the nonwoven materials commonly used as paper products, including tissue paper, from which at least a portion thereof comprises papermaking fibers, which may be selected, without limitation, from the group consisting of: hardwood fibers, softwood fibers, recycled fibers, baggasse fibers, fluff pulp, and natural papermaking fibers, synthetic papermaking fibers, cellulosic fibers, and blends thereof.
The invention also provides an organoclay composition made by the reaction of: (a) one or more clays; and (b) one or more compounds selected from the group consisting of (I) compounds of structural formula (1B) and (ii) compounds of structural formula (2B). In a preferred embodiment of the invention, the clay is a smectite clay selected from the group consisting of bentonite and hectorite. In another preferred embodiment of the invention, component (b) is added in an amount sufficient to react completely with the cation exchange capacity of the clay.
The invention also provides a process for preparing an organoclay composition which comprises: (a) preparing a slurry of one or more clays; (b) heating the slurry to a temperature between 20xc2x0 C. and 100xc2x0 C.; (c) adding to the heated slurry one or more compounds selected from the group consisting of: (I) compounds of structural formula (1B) and (ii) compounds of structural formula (2B). In a preferred method according to the invention, the process further comprises a step (e) recovering and drying the organoclay composition.
Ranges in amounts given for each ingredient or component of a composition or formulation set forth herein in certain circumstances may be theoretically capable of adding up to a sum of greater than 100%. As would be appreciated by those of skill in the art, it is understood that such impossible formulations (that is, those formulations whose component amounts add to a sum greater than 100%) are excluded from the claims and disclosure. For example, a formulation m. m having components A and B, where the amount of A is said to range from 25% to 75% and the amount of B is said to range from 25% to 55%, if containing 65% of A, is understood to have 35% or less of B in that formulation, so that the sum of A and B does not exceed 100%. Thus, all formulations or compositions presented herein whose component amounts add to a sum less than or equal to 100% are understood as being part of the claims and disclosure.
The present invention is directed to novel amine compounds and quaternary compounds, compositions and formulations containing such novel compounds, and uses thereof.
As will be appreciated, a particularly preferred embodiment of the present invention comprises mixtures of Inventive Ester Quats, such that degrees of quaternization or protonation (including unquaternized, unprotonated compounds), degrees of esterification, and chain lengths and molecular weights of different molecules within the mixture will differ such that the respective properties can be represented as an average over all the molecules present in the mixture. In such mixtures, then, properties such as the degree of quaternization can be expressed as average values which may lie between integer whole numbers.
It can be seen that the Inventive Ester Quat structures embrace compounds ranging from compounds wherein no nitrogen atom is quaternized or protonated with a corresponding substituent and compounds wherein every nitrogen atom is quaternized or protonated with a substituent. Furthermore, for Inventive Ester Quats that contain more than one nitrogen atom per molecule, that is, those of structural formulas (2A) and (2B), the term xe2x80x9cpartiallyxe2x80x9d is meant to convey that at least one nitrogen atom on the Inventive Ester Quat molecule does not have a substituent attached to it, and preferred embodiments of the instant invention include Inventive Ester Quats which are partially quaternized or protonated. Thus, the instant invention includes Inventive Ester Quats and mixtures thereof, in which there are either no substituents or the only substituents present are xe2x80x94H. Such substituents can be present in a degree such that all nitrogen atoms are protonated, or fewer than all nitrogen atoms are protonated (xe2x80x9cfullxe2x80x9d and xe2x80x9cpartialxe2x80x9d protonation, respectively). Although many of the teachings and disclosure below uses the terms xe2x80x9cquaternary compoundsxe2x80x9d or xe2x80x9cquatsxe2x80x9d and similar language with respect to applications and formulations including Inventive Ester Quats, such disclosures should be understood to apply equally to the non-quaternized (i.e., ester amine) Inventive Ester Quats, unless specifically and unambiguously excluded.
The acyl groups on the Inventive Ester Quats can all have the same chain lengths. More preferably they have several chain lengths and degrees of carbon-carbon unsaturation, reflecting the fact that the fatty acyl groups can be derived from naturally occurring sources which contain mixtures of fatty acids with differing chain lengths and differing degrees of carbon-carbon unsaturation. Examples of such sources include fatty acids derived from the following sources: tallow, tall oil fatty acid (TOFA), fish oils, canola (including fatty acids derived from partially hydrogenated canola), jojoba, palm, coconut, avocado, wheat germ, rapeseed, olive, orange, corn, linseed, neem, peanut, safflower, sesame seed, soybean, sunflower seed, and cocoa butter. Preferred materials are tallow, canola, and palm.
Further preferred embodiments of Inventive Ester Quats are described herein with respect to the various formulation capabilities of the products of this invention.
Inventive Ester Quats, when quaternized and/or protonated to any degree, include an anion Axe2x88x92 which is present in a number of moles equal to the total positive charge of the nitrogen-containing cation. The anion Axe2x88x92 can represent any anion which is not deleterious to the properties of the overall compound. Non-limiting examples of Axe2x88x92 include fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Preferred examples are chloride, bromide, citrate, acetate, methyl sulfate, ethyl sulfate, and salicylate. If the anion is monovalent (has a charge of xe2x88x921), Axe2x88x92 represents the anion group, if the anion is divalent (has a charge of xe2x88x922), Axe2x88x92 represents half of the anion group, if the anion is trivalent (has a charge of xe2x88x923), Axe2x88x92 represents a third of the anion group, and so on.
Inventive Ester Quats can be used alone or in mixtures, used in combination with other compounds or additives, or used as a formulation with other compounds or additives, depending on the intended use and the advantages and disadvantages attendant with each alternative application method. Some examples of compounds or additives that may be used in conjunction with Inventive Ester Quats or made into formulations with compounds of structural formula Inventive Ester Quats include surfactants or detergents, especially quaternary ammonium compounds, perfumes, preservatives, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, viscosity control agents, antioxidants, silicones, mineral oils and petrolatums, synthetic lubricants, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, and mixtures thereof. Many examples of these additives are set forth in detail and are intended to demonstrate the scope of the invention. Other compounds or additives familiar to those of skill in the art and appropriate to a particular use, however, may also be used with or formulated with Inventive Ester Quats.
Inventive Ester Quats (either alone or in combination with other compounds) have many potential applications. For example, Inventive Ester Quats may be used as detailed herein, without limitation, as a fabric softener (either alone or in a combination detergent/fabric softener), as a car spray microemulsion, as a paper debonder, as a hair or skin conditioner, as a corrosion inhibitor, as an asphalt emulsifier, as an organoclay ingredient, or as an agricultural product emulsifier.
The present disclosure shows that Inventive Ester Quats may be used for many purposes and suitable additives may be incorporated therein based on the ultimate application. Such ingredients, for example, may contribute significantly to the ease of formulation, stability, dispersibility, fluidity, and the performance properties of the compositions.
Inventive Ester Quats have many advantages over the prior art compounds. For example, many of the compositions of the present invention can be produced as a liquid product that is 100% actives and contains no volatile organic compounds (VOCs) as solvents nor do they require low flash solvents for formulations. Such compositions and formulations according to the present invention are water soluble/dispersible, even cold water dispersible; readily formulate with other classes of quaternary amine softener/debonders; are low foaming; are virtually odor free; and are hydrolytically stable and color stable on storage. In addition, as shown below, the compositions of the present invention are extremely effective debonders as measured by tensile reduction and are very hydrophilic, affording very absorbent tissue and towels. Although the compositions of the present invention exhibit a wide range of tissue softening, they do impart softness and certain compounds exhibit effective softening, comparable to commercial softeners, such as AROSURF(copyright) PA-801 available from Witco Corporation. Furthermore, as there are two fatty ester functionalities in the compositions of the present invention, they exhibit improved biodegradability.
In one aspect, the present invention provides compounds and formulations that have the ability to impart to paper and paper products bulk enhancement, softness, lubricity, and antistatic properties, and improve ease of handling of the substrate and surface appearance; in the papermaking process, such compounds of the present invention are termed debonders. Debonders are usually added to the aqueous slurry of paper fibers in the head tank or headbox of a papermaking machine just prior to feeding the resulting slurry onto the papermaking or dewatering screen. These debonders condition the fibers to give improved softness feeling to the paper fibers that is valuable for their use in tissue and towelmaking. The compositions and formulations of the present invention can also be incorporated into the paper or tissue by any suitable means such as spraying or printing onto the surface of the paper or tissue. Given the surprisingly low viscosities of the Inventive Ester Quats alone or in many formulations, as mentioned above, spraying or topical application of the Inventive Ester Quats, even neat, is particularly suitable. If the Inventive Ester Quats are applied without the presence of water or other solvent, no evaporation need occur and the possibility of wrinkling is avoided.
Moreover, the present invention provides compounds and formulations that have the ability to impart to fabric (that is, articles of clothing, textiles, and so forth), properties including softness to the touch, ease of handling, increased lubricity, and a reduced tendency to carry or pick up static electricity. One form in which the compounds and formulations of the present invention are provided is as a liquid, for instance, as an emulsion or as a solution/suspension of the desired components. During use, an appropriate controlled amount of the liquid formulation is employed, for example, by pouring the formulation directly into the washing machine. Typically, the formulation is dispensed during the rinse cycle of the washing machine, either poured in by hand or metered in by an appropriate automatic metering device with which the washing machine is equipped.
The present invention also provides compounds and formulations that are useful in personal care products such as hair or skin conditioners. In this application, the present invention provides formulations that impart softness, lubricity, and improve the surface appearance of the skin or hair. The hair conditioners additionally reduce the tendency for tangling, improve the manageability, and impart a soft feel to the hair strands. Such hair conditioners are applied as dilute emulsions to the hair following its wash or may be incorporated into a combined conditioner and shampoo composition, also known as a conditioning shampoo, two-in-one shampoo, or two-in-one. Such hair and skin conditioning formulations typically incorporate effective amounts, for example, 0.1 wt. % to 10 wt. % or more, of emollients, humectants, and/or slip and conditioning agents, such as organopolysiloxanes and the like, to create formulations that are monophasic and can be made to be translucent or even clear. Compounds suitable for use as emollients, humectants and conditioners in formulations for skin care or hair care can be found in the CTFA Cosmetic Ingredient Dictionary, 3d Edition, and in the CTFA Cosmetic Ingredient Handbook, which are hereby incorporated by reference in their entireties.
Inventive Ester Quats are expected to be particularly useful in applications that take advantage of their ability to disperse hydrophobic material and to enhance the penetration and wetting exhibited by the compositions. Examples of such compositions and applications are set forth below, each revealing an additional aspect of the present invention.
The compounds and formulations of the present invention may be used as oil dispersants and oil slick dispersant formulations for application onto oil, for example, onto a film of oil, to disperse the oil.
The compounds and formulations of the present invention may also be used as oil well stimulation and oil recovery aids for injection into oil wells in order to penetrate into the surface of the borehole and assist liberation of crude oil from the matrix material into the borehole, from which it can be brought to the surface.
In addition, the compounds and formulations of the present invention may be used as vehicles for hydrophobic sheeting agents such as mineral oil and silicone oil. Such oils can readily be dispersed in compositions, according to the present invention, and the resulting formulations are highly satisfactory when sprayed or otherwise applied to a surface, such as a freshly washed automobile surface, to impart a lustrous, water-repellent film to the surface.
The compounds and formulations of the present invention may also be used as rinse aids, such as used in automatic dishwashers, wherein application of the composition of the present invention disperses residual hydrophobic matter, including cleaner residues and films.
Furthermore, the compounds and formulations of the present invention may be used as paper deinking and ink flotation agents for treating waste inked paper by addition to the pulp slurry such that the ink is liberated from the paper and prevented from redepositing onto the paper. In this application, the ink is typically dispersed or even fully solubilized in the resulting solution when the ink particles are floated from the fibers.
The compounds and formulations of the present invention may also be used as asphalt emulsion agents for emulsifying finely divided asphalt (at loadings of typically 1-20 wt. %), with or without particulate filler such as, in an aqueous phase, which comprises the composition according to the present invention.
Moreover, the compounds and formulations of the present invention may be used as corrosion inhibitor agents for application to any surface to which one desires to apply a film that protects against corrosion. The composition would typically contain an effective amount of a hydrophobic corrosion inhibiting material, such as liquid or waxy-solid fatty ester, paraffinic hydrocarbon, silicone, or the like, dispersed in a composition according to the present invention.
In addition, the compounds and formulations of the present invention may be used with ore flotation agents for separating ore from rock. Such floatation agents might include, for example, the agent available from Witco Corporation under the tradename WITCAMINE(copyright) AL42-12. Typically, the ore floatation agent (a collector or frother, depending on the characteristics of the particular separation desired in the floatation cell) or mixture thereof, which is a relatively hydrophobic material, is dispersed in a composition according to the invention and an effective amount is added (on a batch or continuous basis) to the ore separation cell. This permits the formulator to improve the dispersibility of the hydrophobic ore floatation agent, which often improves the performance of the mineral separation by improving the efficiency of the floatation agent""s dispersibility. This can enable the operator to use smaller amounts of the ore floatation agent to achieve the desired purpose because there is a higher concentration of active ingredients available.
In addition, the compounds and formulations of the present invention may be used as suspension concentrates and emulsifiable concentrates of herbicides, pesticides, miticides, fungicides, or bactericides, wherein one or more liquid or solid, generally hydrophobic, active ingredients are dispersed in a composition according to the present invention. The resulting concentrate can be applied as a concentrate on or around desired vegetation, but is more often mixed with water (for example, at the point of use) to form a final dilute formulation having the desired concentration of active ingredient(s). This application takes advantage of the noteworthy property of this invention that addition of the water does not disrupt the monophasic state, nor the fluidity, of the formulation.
Furthermore, as noted above and explained in more detail below, organoclays or organophilic clays prepared from Inventive Ester Quats and clays, and the processes for making such organoclays are an aspect of the instant invention.
As noted above, the compositions and formulations of the present invention can also optionally contain other components, depending on the additional properties one may wish to provide in the finished composition. Such additional components include, but are not limited to, additional coupling agents and solvents, additional quaternary ammonium compounds, additional surfactants, hydrocarbon actives, perfumes, preservatives including bacteriocides and fungicides, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, viscosity control agents, antioxidants, silicones, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, aloe, humectants, skin protectants, feel modifiers, and mixtures thereof. Examples of these additional components are set forth below, with the understanding that such additives or additional components mentioned herein are not exclusive to any particular application or use, but appropriate additives or additional components may be selected depending the application. Thus glycerin may be incorporated in the formulations of the instant invention to provide a hair conditioner or to provide a skin-conditioning lotion to be incorporated into a tissue to produce a tissue impregnated with the lotion.
Inventive Ester Quats can easily be synthesized from readily available starting materials using reaction procedures and conditions quite familiar to those of ordinary skill in this art. A preferred synthesis method is set forth below. As would be well-known in the art, other synthetic procedures or variations on the preferred synthetic procedure set forth below may be used that are more or less efficient or cost-effective than this proffered procedure. Such variations may include, without limitation, substitutions of reagents, starting materials, or catalysts; different amounts or concentrations of reactants, starting materials, or catalysts; different reaction conditions or duration of reactions; different analytical procedures or points at which a reaction is deemed complete; the isolation or purification of reaction products at any step; automation of the synthesis procedure; and substitution of different reaction(s) for one or more of the reactions set forth below. As one of skill in the art would appreciate, organic reactions generally do not produce stoichiometrically pure products and the actual product of an organic reaction is often a mixture of products. The reactions called for and the products specified therefore indicate the major or desired reaction or product.
In one embodiment, the synthesis begins with a primary fatty amine derived from a fatty acid and ammonia and hydrogen, such as a primary tallow amine, primary oleyl amine, primary canola amine (available from Witco Corporation under the ADOGEN(copyright) tradename) or a fatty diamine from reaction of a fatty amine and acrylonitrile followed by reduction with hydrogen.
In the first step, this fatty amine compound is alkoxylated using an alkoxylating agent, which may be ethylene oxide (EO), propylene oxide (PO), or butylene oxide (BO), or (less preferred) a mixture thereof, depending on the desired choice of alkyl groups to become attached to the respective nitrogen atoms. In a preferred procedure used to synthesize the examples presented herein, the initial alkoxylation step is performed at 160-165xc2x0 C. with no catalyst, after an induction period of about 30 minutes, the reaction starts when all calculated alkoxylating agent needed to react with the protons on the nitrogen groups is added. The reaction is allowed to proceed for 30 minutes and is then analyzed; if the tertiary amine is between 92 wt. % and 97 wt. %, the reaction is deemed complete and 0.1% solids, based upon the sum of final charges, of KOH as a 45% aqueous solution is added to the mixture. The mixture is then dehydrated to remove water, generally to a level of about 200 ppm water. Additional alkoxylating agent is added to achieve the desired molecular weight and the products is tested using the standard xe2x80x9cneutralization equivalentsxe2x80x9d titration method.
In the next step, the alkoxylated product is esterified by reaction of fatty acids with the respective hydroxyl groups resulting from the alkoxylation (where R4 is C15-C17, this product has been assigned CAS Registry Number 217813-05-3). The esterification is carried out with carboxylic acids of structural formula R4C(O)OH, wherein R4 is a linear, branched, or cyclic alkyl or alkylene group containing 11 to 21 carbon atoms. While the esterification can be carried out with an appropriate quantity of one such carboxylic acid, it is preferred for reasons of economy, product performance, and convenience to employ mixtures of carboxylic acids each corresponding to structural formula R4C(O)OH. For instance, mixtures of such fatty acids from various animal and vegetable origins are conveniently commercially available. One example of such material is tallow fatty acids which, as is generally known in this field, is a mixture of fatty acids predominantly composed of fatty acids containing 14, 16, and 18 carbon atoms, and 0 and 1 degrees of unsaturation. Other preferred sources include coconut fatty acids and canola fatty acids, although any suitable fatty acid may be used. Esterification is carried out under conventional conditions, well-known to the chemist in this field, allowing for the withdrawal of by-product water. The number of moles of fatty acid is selected to provide the desired average degree of esterification in the mixture of products formed upon esterification. In a preferred procedure used to synthesize the examples presented herein, the desired amount of fatty acid is added to the alkoxylated ester of the previous step and hypophosphorous acid (HPPA) is added as a catalyst. Preferably, the HPPA is used at a dosage of 0.025 wt. % based on the fatty acid charge; at this dosage, the HPPA also has a bleaching effect on the product. The amount of HPPA used, however, may be adjusted upward or downward and may be eliminated entirely. The reaction mixture is heated to 200xc2x0 C. and a nitrogen sparge is employed to remove the by-product water of reaction. The reaction is monitored for 8-15 hours using a standard xe2x80x9cacid valuexe2x80x9d titration method. When an acid value of 10 is reached, preferably 5 or less, the reaction is deemed complete.
Next, if desired, the esterified product or mixture of esterified products is quaternized and/or protonated. As recognized hereinabove, the esterified product can be completely quaternized, but it is preferred to carry out partial quaternization only, if any. Quaternization is carried out under conditions well known in this field for quaternization of amines, by reaction of the esterified amine with a suitable quaternizing agent. Preferably, only one particular quaternizing agent is employed, in which case all of the quaternizing substituents will be the same. Preferred quaternizing agents include methyl chloride, dimethyl sulfate (DMS), and diethyl sulfate (DES). The DMS derivative has been assigned CAS Registry Number 217813-30-4. In a preferred procedure used to synthesize the examples presented herein, the reaction mixture from the previous step was cooled to 60-70xc2x0 C. and the quaternizing agent was added when the reaction mixture was less than 70xc2x0 C. until the wt.% of free amine was less than or equal to 3.0.
Protonation, if desired, can be carried out by reacting the esterified product or mixture of products with an acid of the formula HA, such as strong acids, such as sulfuric acid, phosphoric acid, or hydrochloric acid, or other acids, such as acetic acid. The acetic acid derivative has been assigned CAS Registry Number 217813-07-5. Optional steps include a bleaching step using bleaching agents well-known in this field.
Each of the foregoing reactions can be carried out in solvent or in solvent-free conditions, in each case employing conditions well established for the respective reactions in this field.
In another embodiment, the Inventive Ester Quats are prepared in a similar manner except that a primary amine containing a C1 to C7 hydrocarbyl group is employed and the caboxylic acid may comprise a compound wherein R4 is a C3 to C10 hydrocarbyl group.
As can be seen, Inventive Ester Quats can readily be synthesized from readily available starting materials using individual reaction procedures and conditions quite familiar to those of ordinary skill in this art.
Examples of particular synthetic procedures would be as follows.
A primary tallow amine, ADOGEN(copyright) 170, was reacted with 10 moles of ethylene oxide per mole of ADOGEN(copyright) 170 to produce VARONIC(copyright) T-210. The VARONIC(copyright) T-210 was then esterified with a mixture of C14-C18 fatty acids, 1.8 moles of fatty acid per mole of ethoxylate, following which the amine ethoxylate ester was quaternized with one mole of DMS. In one example, Example A-1, the fatty acids were a commercial mixture of tallow fatty acids, DISTAL 51. In another example, Example A-2, the fatty acids were obtained from canola oil. Both products were clear liquids at 100% actives.
A primary cocoamine, ADOGEN(copyright) 160, was reacted with 15 moles of ethylene oxide per mole of ADOGEN(copyright) 160 to produce VARONIC(copyright) K-215. The VARONIC(copyright) K-215 was then esterified with a mixture of C14-C18 fatty acids, 1.8, moles of fatty acid per mole of ethoxylate, following which the amine ethoxylate was quaternized with one mole of DMS. In one example, Example 2-A, the fatty acids were a commercial mixture of tallow fatty acids, DISTAL 51. In another example, Example 2-B, the fatty acids were obtained from canola oil. Both products were clear liquids at 100% actives.
A primary canola amine was reacted with 6 moles of ethylene oxide per mole of amine to produce the ethoxylated amine. The ethoxylated amine was then esterified with a mixture of C14-C18 canola acids, 1 mole of acid per mole of ethoxylate. The product could be used as is, could be converted into an ammonium salt by reaction with HCl or acetic acid, or reacted with DMS to form a quaternary ammonium salt.
A fatty diamine, ADOGEN(copyright) 570, was reacted with 10 moles of ethylene oxide per mole of ADOGEN(copyright) 570 to produce VARONIC(copyright) T-410. The VARONIC(copyright) T-410 was then esterified with a mixture of C14-C18 fatty acids. In Example D-1, the fatty acids were a commercial mixture of tallow fatty acids, and the mole ratio of the fatty acids to tallow diamine ethoxylate was 1.5 to 1. The ester of the tallow amine ethoxylate was quaternized with 1.2 moles of DMS. In Example D-2, the fatty acids were obtained from canola oil, and the mole ratio of the fatty acids to tallow diamine ethoxylates was 2/1. The ester of the tallow amine ethoxylate was quaternized with 2 moles of DMS.
Many Inventive Ester Quats have been synthesized and tested in various applications and formulations and the results set forth below. In order to identify such Inventive Ester Quats and certain other commercial compounds and formulations discussed herein, a unique designation has been applied to each, as set forth as a legend in Table 1, which serves to identify the compound being discussed, whether the Inventive Ester Quat 5455-111, or a commercial product, such as that sold by Witco Corporation under the tradename VARISOFT(copyright) 3690.
Preferred Inventive Ester Quats include 5455-63 (VARONIC(copyright) T-210+2 moles canola fatty acid), 5455-158 (canola amine+6 EO+1.5 canola fatty acid), most preferably, 545564 (VARONIC(copyright) T-210+2 moles canola fatty acid+1 mole DMS), 5455-112 (canola amine+6 EO+1 mole canola fatty acid+1 mole DMS), 5455-159 (canola amine+6 EO+1.5 moles canola fatty acid+1 mole DMS), 5398-5/5398-53 (VARONIC(copyright) T-215+1.8 moles tallow fatty acid+1 mole DMS), which can be made according to the above synthesis methods.
The Inventive Ester Quats as described herein exhibit a number of desirable properties making the Inventive Ester Quats particularly suitable for formulation into commercial products such as paper debonders, fabric softeners and other commercial products, as mentioned above.
Most notably, the Inventive Ester Quats can readily be formulated into useful compositions such as aqueous compositions, which achieve the desired functionality and which are clear, that is, transparent or translucent. This property can be realized at a variety of concentrations of active ingredient, with or even without special solvents or coupling agents. In some cases, the Inventive Ester Quats are colored after synthesis, but they can be bleached using techniques and methods known to those of skill in the art. The Inventive Ester Quats, however, are very color stable on storage, as shown in Table I. It should be noted that these Inventive Ester Quat preparations were not color bleached before testing, which is contemplated for certain applications.
The Inventive Ester Quats are also very hydrolytically stable on storage, as shown in Table II. The Inventive Ester Quats were prepared as 5 wt. % solutions in 50% isopropyl alcohol/50% water; the color stability and absence of pH drift showed that the Inventive Ester Quats are generally quite hydrolytically stable.
Other properties are realized as well. For instance, as noted above, the products are ultimately biodegradable. Surprisingly, the embodiments which have no substituents, or wherein the only substituents are xe2x80x94H, exhibit satisfactory biodegradability. Also, the Inventive Ester Quats exhibit advantageous stability, solubility, and freedom from excessively objectionable color, odor, and foam. Furthermore, the Inventive Ester Quats alone or in many formulations often exhibit surprisingly low viscosities compared to conventional amine or quaternary ammonium compounds, making the Inventive Ester Quats particularly suitable for certain methods of application or use, for example, spraying or topical application of the Inventive Ester Quats.
Although the Inventive Ester Quats have many potential uses, in particular, they exhibit highly satisfactory fabric softening capabilities. Thus, the Inventive Ester Quats, as well as mixtures of such compounds, can be advantageously formulated appropriately into products useable as fabric softeners. It has been found that, regardless of the other components that may be present in the fabric softener formulation, the pH of the formulation as a whole should be below 5, and preferably 2.5 to 4.0, in order to maintain low susceptibility of the ester functionality to hydrolysis in water. The preferred method for providing or adjusting the desired pH value is adding small amounts of an acid, such as hydrochloric acid, sulfuric acid, or acetic acid, consistent with appropriate adjustment of the average degree of esterification and average degree of quaternization to the Inventive Ester Quats. Preferred emulsions useful as fabric softener compositions can contain about 2 wt. % to about 80 wt. %, preferably 5 wt. % to 30 wt. %, and more preferably 6 wt. % to 25 wt. %, of one or more Inventive Ester Quats. In general, higher solids contents can be provided more easily with lower degrees of quaternization.
The Inventive Ester Quats can be formulated into compositions that may include water and one or more of the solvents which are conventionally used, including ethanol, isopropanol, hexylene glycol, propylene glycol, diethylene glycol, or similar solvent of mixture thereof, as a concentrate or more dilute form, depending on the application. Selection of a suitable solvent for a particular application is well-known to those of skill in the art. However, as the majority of the Inventive Ester Quats are liquids at 100% actives, solvents are not required for formulations using these Inventive Ester Quats. This aspect of the present invention advantageously avoids the use of solvents which have low flash points, which contribute to VOC loads and which contribute to BOD load.
Additional conventional quaternary ammonium compounds or salts may be present with the compound or Inventive Ester Quats in accordance with the present invention. The compounds presented below are only examples of conventional quaternary compounds that are suitable for use in the formulations of the present invention. As with the Inventive Ester Quats, these conventional quaternary ammonium compounds (quats or salts) may have an anion to provide electrical neutrality and, in general, such anion may be any anion which is not deleterious to the properties of the overall compound. Thus, in the structural formulas (i) to (xxiv) below, the counteranion, whether designated as Axe2x88x92 or not shown but understood, may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, citrate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Preferred examples of the anions are chloride, bromide, methyl sulfate, ethyl sulfate, acetate, citrate, and salicylate. If the anion is monovalent (has a charge of xe2x88x921), Axe2x88x92 represents the anion group, if the anion is divalent (has a charge of xe2x88x922), Axe2x88x92 represents half of the anion group, if the anion is trivalent (has a charge of xe2x88x923), Axe2x88x92 represents a third of the anion group, and so on.
In general, the amounts of Inventive Ester Quats and conventional quaternary compounds in a formulation can vary from 100% Inventive Ester Quat (i.e., neat) to less than about 1% Inventive Ester Quat and remainder conventional quaternary compounds or a mixture of conventional quaternary compounds and other surfactants, solvents, and additives. The amount of conventional quaternary ammonium compound is therefore any effective amount for the purpose. In general, the amount of Inventive Ester Quat will be substantial in any formulation, particularly with respect to the total amount of quaternary ammonium compounds, which is the sum of the Inventive Ester Quats and the conventional quaternary ammonium compounds, in the composition. In general, it is contemplated that Inventive Ester Quats may be formulated with conventional quaternary ammonium compounds, alone or in combination with other additives set forth herein, such that the Inventive Ester Quats comprise from about 10% to about 99% by weight, preferably from about 15% to about 95% by weight, more preferably from about 30% to about 90% by weight, even more preferably from about 50% to about 90% by weight, and most preferably from about 75% to about 90% by weight, of the total amount of quaternary ammonium compounds in the composition.
The conventional quats that may be formulated with the Inventive Ester Quats in accordance with the present invention include, but are not limited to, nitrogenous compounds selected from the group consisting of quaternized or acid salt derivatives of:
(i) alkylene diamines, diamides, and amidoamines, including compounds of the formula: 
wherein each R1 is a C12-C21 alkyl or alkylene group, each Z is m xe2x80x94(R2O)0-4H, or xe2x80x94R2H, and R2 and R3 are divalent C1-C6 alkylene groups;
(ii) substituted imidazoline compounds having the formula: 
(iii) reaction products of higher fatty acids with alkylenetriamines in, for example, a molecular ratio of about 2:1, the reaction products containing compounds of the formula: 
wherein R1, R2 and R3 are defined as above; and
(iv) substituted imidazoline compounds having the formula: 
wherein G is xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94 and R1 and R2 are defined as above; and mixtures thereof.
Preferred examples of compounds of structural formula (i) are those derived from hydrogenated tallow fatty acids and the hydroxyalkylalkylenediamine is N-2-hydroxyethylethylenediamine, such that R1 is a C15-C21 aliphatic group, and R2 and R3 are divalent ethylene groups.
Preferred examples of compounds of structural formula (iii) are stearic hydroxyethyl imidazoline, wherein R1 is a C21 aliphatic group and R2 is a divalent ethylene group, and N,Nxe2x80x3-ditallowalkanoyldiethylenetriamine, where R1 is a C15-C21 aliphatic group and R2 and R3 are divalent ethylene groups. A preferred example of a compound of structural formula (iv) is 1-tallowamidoethyl-2-tallowimidazolin wherein R1 is a C15-C2, aliphatic group and R2 is a divalent ethylene group.
Both N,Nxe2x80x2-ditallowalkanoyldiethylenetriamine and 1-tallowethylamido-2-tallowimidazolin are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see xe2x80x9cCationic Surface Active Agents as Fabric Softeners,xe2x80x9d R. R. Egan, Journal of the American Oil and Chemicals Society, January 1978, pages 118-121). N,Nxe2x80x3-ditallowalkanoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Corporation. Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is available from Witco Corporation under the tradename VARISOFT(copyright) 475.
Other suitable quats are those containing one C18-C22 aliphatic group, particularly those selected from the group consisting of:
(v) acyclic quaternary ammonium salts having the formula: 
wherein R4 is a C8-C22 aliphatic group, benzyl or (C4-C18 alkyl)-OCH2CH2)2-3xe2x80x94, R5 and R6 are C1-C4 alkyl or hydroxyalkyl groups, and Axe2x88x92 is an anion as defined above;
(vi) substituted imidazolinium salts having the formula: 
wherein R1 is a C12-C21 alkyl or alkylene group, R7 is hydrogen or a C1-C4 alkyl or hydroxyalkyl group, and Axe2x88x92 is an anion as defined above;
(vii) substituted imidazolinium salts having the formula: 
wherein R1, R2, R5, and Axe2x88x92 are as defined above;
(viii) alkylpyridinium salts having the formula: 
wherein R4 is a C8-C22 aliphatic group and Axe2x88x92 is an anion as defined above; and
(ix) alkanamide alkylene pyridinium salts having, the formula: 
wherein R1 is a C12-C21 aliphatic group, R2 is a divalent C1-C6 alkylene group, and Axe2x88x92 is an anion as defined above; and mixtures thereof.
Examples of compounds of structural formula (v) are the monoalkyltrimethylammonium salts such as monotallowtrimethylammonium chloride, mono(hydrogenated tallow)-trimethylammonium chloride, palmityltrimethylammonium chloride and soyatrimethylammonium chloride, available from Witco Corporation under the tradenames ADOGEN(copyright) 471, ADOGEN(copyright) 441, ADOGEN(copyright) 444, and ADOGEN(copyright) 415, respectively. In these compounds, R4 is a C16-C18 aliphatic group, and R5 and R6 are methyl groups. Other examples of compounds of structural formula (v) are behenyltrimethylammonium chloride, wherein R4 is a C22 aliphatic group, which is available from Witco Corporation under the tradename KEMAMINE(copyright) Q2803-C; soyadimethylethylammonium ethylsulfate, wherein R4 is a C16-C18 aliphatic group, R5 is a methyl group, R6 is an ethyl group, and Axe2x88x92 is an ethylsulfate anion; and methyl bis(2-hydroxyethyl)octadecylammonium chloride wherein R4 is a C18 aliphatic group, R5 is a 2-hydroxyethyl group and R6 is a methyl group.
An example of a compound of structural formula (vii) is 1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfate, wherein R1 is a C17 aliphatic group, R2 is an ethylene group, R5 is an ethyl group, and Axe2x88x92 is an ethylsulfate anion.
Other quats useful in the present invention include cationic nitrogenous salts having two or more C8-C22 aliphatic groups or one C8-C22 aliphatic group and an arylalkyl group. Examples include:
acyclic quaternary ammonium salts having the formula: 
wherein each R4 is a C8-C22 aliphatic group, R5 is a C1-C4 alkyl or hydroxyalkyl group, R8 is selected from the group consisting of R4 and R5 groups, and Axe2x88x92 is an anion as defined above;
(xi) diamido quaternary ammonium salts having the formula: 
wherein each R1 is a C12-C21 alkyl or alkylene group, each R2 is a divalent alkylene group having 1 to 3 carbon atoms, R5 and R9 are C1-C4 saturated alkyl or hydroxyalkyl groups, and Axe2x88x92 is an anion as defined above;
(xii) alkoxylated diamido quaternary ammonium salts having the formula: 
wherein n is equal to 1 to about 5, and R1, R2, R5, and Axe2x88x92 are as defined above;
(xiii) quaternary ammonium compounds having the formula: 
wherein R4 is a C8-C22 aliphatic group, each R5 is a C1-C4 alkyl or hydroxyalkyl group, and Axe2x88x92 is an anion as defined above;
(xiv) amide-substituted imidazolinium salts having the formula: 
wherein each R1 is a C12-C21 aliphatic group, R2 is a divalent alkylene group having 1 to 3 carbon atoms, and R5 and Axe2x88x92 are as defined above, or R5 is xe2x80x94H; and
(xv) ester-substituted imidazolinium salts having the formula: 
wherein R1, R2, R5, and Axe2x88x92 are as defined above; and mixtures thereof.
Examples of compounds of structural formula (x) are the well-known dialkyldimethylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, di(hydrogenated tallow)dimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride. Di(hydrogenated tallow)dimethylammonium chloride and ditallowdimethylammonium chloride are preferred. Examples of commercially available dialkyldimethylammonium salts usable in the present invention are di(hydrogenated tallow)dimethylammonium chloride (available from Witco Corporation under the tradename ADOGEN(copyright) 442); ditallowdimethylammonium chloride (available from Witco Corporation under the tradename ADOGEN(copyright) 470); distearyldimethylammonium chloride (available from Witco Corporation under the tradename AROSURF(copyright) TA-100); dicocodimethyl ammonium chloride (available from Witco Corporation under the tradename ADOGEN(copyright) 462), and dibehenyldimethylammonium chloride,h wherein R4 is an acyclic aliphatic C22 aliphatic group (available from Witco Corporation under the tradename KEMAMINE(copyright) Q-2802C).
Examples of compounds of structural formula (xi) are methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate, wherein R1 is a C15-C17 aliphatic group, R2 is an ethylene group, R5 is a methyl group, R9 is a hydroxyalkyl group, and Axe2x88x92 is a methylsulfate anion; both of these materials are available from Witco Corporation under the tradenames VARISOFT(copyright) 222 and VARISOFT(copyright) 110, respectively.
An example of a compound of structural formula (xiii) is dimethylstearylbenzylammonium chloride, wherein R4 is a C18 aliphatic group, R5 is a methyl group and Axe2x88x92 is chloride, which is available from Witco Corporation under the tradename VARISOFT(copyright) SDC.
Examples of compounds of structural formula (xiv) are 1-methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate and 1-methyl-1-(hydrogenated tallowamidoethyl)-2-(hydrogenated tallow)imidazolinium methylsulfate wherein R1 is a C15-C17 aliphatic group, R2 is an ethylene group, R5 is a methyl group, and Axe2x88x92 is a chloride anion; available from Witco Corporation under the tradenames VARISOFT(copyright) 475 and VARISOFT(copyright) 445, respectively.
Additional examples of quaternary ammonium compounds useful in the present invention include:
(xvi) compounds having the formula: 
wherein R11 is selected from the group consisting of: (a) xe2x80x94CH3, xe2x80x94CH2CH3, xe2x80x94CH2CH2OH, or C12-C24 linear aliphatic groups, (b) ether groups, each of which has the structure: R13O(CH2O)yxe2x80x94, (c) amide groups, each of which has the structure: 
and (d) ester groups, each of which has the structure: 
wherein R12 is a C8-C32 linear aliphatic group, R13 is a C8-C2, linear aliphatic group, R4 is a C7-C17 linear aliphatic group, Z is an alkoxy group containing one oxygen atom and either two or three carbon atoms, Axe2x88x92 is an anion as defined above, m is an integer from 1 through 12, and y is an integer which is either 2 or 3.
Yet additional examples of fabric softening compounds useful in the present invention include:
(xvii) compounds having the formula: 
wherein R15 is hydrogen or a C1-C4 alkyl group, each R16 is a C1-C4 alkyl group or 
each R17 is a C8-C28 alkyl or alkenyl group, R18 is hydrogen or a C1-C4 alkyl group, each y is 0 or 1, x is 0 or 1, and each n is from 1 to 6;
(xviii) amides represented by the structural formula: 
wherein R19 and R20 are selected independently from the group consisting of C1-C22 aralkyl or alkaryl groups, R21 is hydrogen, a C1-C22 aralkyl or alkaryl group, or is Oxe2x80x94R22, wherein R22 is a C1-C22 aralkyl or alkaryl group, and R21 and R22 optionally contain 1 to 10 alkylene oxide units or functional groups selected from hydroxy, amine, amide, ester, and ether groups; the aryl groups being possibly derived from heterocyclic compounds; at least one of the R19 and R20 groups contains 10 or more carbon atoms; and where the sum of carbon atoms in R19+R20+R21 is equal to or greater than 14. Preferably, the sum of carbon atoms in R19+R20 is equal to or greater than 16.
Examples of compounds of structural formula (xviii) include N,N-ditallow acetamide, N,N-dicoconut acetamide, N,N-dioctadecyl propanamide, N-dodecyl-N-octadecyl acetamide, N-hexadecyl-N-dodecyl butanamide, N,N-ditallow benzamide, N,N-dicoconut benzamide, and N,N-ditallow 2-phenyl acetamide.
Additional fabric softening compounds useful in the present invention include all ester quaternaries, including but not limited to:
(xix) compounds of the following structural formulas: 
wherein each R21 is independently a C12-C22 aliphatic group; each Q21 is independently a C1-C4 alkyl group, benzyl, xe2x80x94CH2CH2OH, xe2x80x94CH2CH(OH)CH3, or R21xe2x80x94C(O)xe2x80x94(Oxe2x80x94(Alk21))1-4; each Alk21 is independently C2H4, C3H6 or C4H8; and Axe2x88x92 is an anion as defined above;
(xx) compounds of the formula: 
wherein each A22 is independently a C1-C3 alkyl, benzyl, or Hxe2x80x94Alk22xe2x80x94O)1-3xe2x80x94Alk22xe2x80x94, wherein each Alk22 represents xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94, or xe2x80x94CH2CH(CH3)xe2x80x94, provided further that one of the A22 can be hydrogen; D is methyl, ethyl, propyl, xe2x80x94CH2)1-3COOxe2x80x94, benzyl or hydrogen; i is 0 or 1 and j is 0 or 1, provided that the sum of (i+j) is 1 or 2; each X22 is a C11-C23 aliphatic group containing up to 3 carbon-carbon double bonds; n is two minus the number of xe2x80x94CH2)1-3COOxe2x80x94 substituents present; and Axe2x88x92 is an anion as defined above;
(xxi) compounds of the formula:
R23xe2x80x94[C(O)O(CH2)1-5]0-1xe2x80x94C(O)NH(CH2)2-5xe2x80x94N(R23a)(R23b)xe2x80x94(CH2)2-5xe2x80x94OC(O)R23Axe2x88x92
wherein each R23 is independently a C8-C22 alkyl or alkenyl group; R23a is a C1-C3 straight or branched alkyl or hydroxyalkyl group, benzyl, or xe2x80x94C2H4OC(O)R26, wherein R26 is a C8-C22 straight or branched alkyl or alkenyl group; R23b is xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5, or benzyl; and Axe2x88x92 is an anion as defined above; and
(xxii) compounds of the following structural formulas: 
wherein each R24 is independently a C1-C8 straight or branched alkyl or alkenyl containing 0 to 3 hydroxyl groups; each R25 is a C10-C22 straight or branched alkyl or alkenyl group containing 0 to 3 hydroxyl groups; each Y is xe2x80x94Oxe2x80x94C(O)xe2x80x94 or xe2x80x94C(O)xe2x80x94Oxe2x80x94; each m is 1 to 3; each n is from 1 to 8; and Axe2x88x92 is an anion as defined above.
Preferred examples of compounds of structural formulas (xxii) include methyl diethanolamine (MDEA) ester quats, triethanolamine (TEA) ester quats, for example, di(tallow carboxyethyl) hydroxyethyl methylammonium methosulfate, available from Witco Corporation under the tradename REWOQUAT(copyright) WE 16, or epichlorohydrin-based ester quats, all of which are used and accepted as fabric softeners worldwide because of their favorable biodegradation profiles, but usually lack the optimum softening performance of other quats.
Additional compounds useful in the present invention include polyester polyquaternary compounds, including but not limited to:
(xxiii) compounds of the following structural formula: 
wherein each of R* and R** is independently a linear, branched or cyclic alkylene group containing 2 to 12 carbon atoms, wherein no two nitrogen atoms are separated by fewer than 2 carbon atoms;
each of A1, A2, A3, A4, and A5 is independently a straight or branched alkylene containing 2 to 4 carbon atoms;
each of R26, R27, R28, R29, and R30 is independently xe2x80x94H or RAC(O)xe2x80x94 wherein RA is straight or branched alkyl or alkenyl containing 7 to 21 carbon atoms and 0 to 4 carbon-carbon double bonds; provided that at least one of R26, R27, R28, R29, or R50 is RAC(O)xe2x80x94; each of Q1, Q2 and Q3 is independently xe2x80x94H, CH3, C2H5, xe2x80x94C3H7, xe2x80x94C4H5, benzyl, xe2x80x94CH2COOH, or xe2x80x94CH2COOXxe2x88x92; or, if R* is a xe2x80x94CH2CH2xe2x80x94 group, Q1 and Q3 together or Q1 and Q2 together may be a xe2x80x94CH2CH2xe2x80x94 group to form a six-membered piperazine ring; or, if R** is a xe2x80x94CH2CH2xe2x80x94 group, Q3 and Q3 together may be a xe2x80x94CH2CH2xe2x80x94 group to form a six-membered piperazine ring; m is 0 to 4; r is 0 to 2; each of v, w, x, y, and z is independently 1 to 8; i is 0 to 1, j is 0 to 1, and each k is 0 to 1, and the sum of (i+j+k) is 0 to 4; each Xxe2x88x92 is independently an anion that may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like; and n is the number of moles of Xxe2x88x92 needed to give the compound of structural formula (xxiii) a zero net charge. Compounds of structural formula (xxiii), formulations thereof, and uses thereof, form the subject matter of pending U.S. application Ser. No. 09/170,623, filed on Oct. 13, 1998, which is incorporated by reference in its entirety; and
(xxiv) compounds of the following structural formulas: 
wherein R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5;
R1, R2, and R3 are each independently of one another fatty acid radicals having 6-22 carbon atoms; and Xxe2x88x92 is an inorganic or organic anion that may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Compounds of structural formula (xxiv), formulations thereof, and uses thereof, form the subject matter of pending PCT application No. PCT/US99/00213, filed on Jan. 6, 1999 and pending PCT application No. PCT/US99/00295, filed on Jan. 7, 1999, both of which are incorporated by reference in their entireties.
In a preferred embodiment of this invention, Inventive Ester Quat formulations may be formulated using an appropriate amount of one or more straight or branched alkyl diols containing 4 to 12 carbon atoms, and/or alkoxylates of such diols with up to 40 alkoxy units per diol moiety, wherein the alkoxylate chains are composed of alkoxy units which are ethoxy, propoxy or butoxy or mixtures thereof, and preferably ethoxy or propoxy. These diol and diol alkoxylate hydrotropes or coupling agents are added to the formulations to increase the amount of the relatively water-insoluble surfactants that can be solubilized into the system. In most cases, they do not act as surfactants to lower surface tension, but they often allow surfactants in the presence of salts or electrolytes to be added and subsequently dispersed into water at higher concentrations or at lower viscosities of the formulation than is otherwise achieved using only surfactant and water. These coupling agents assist surfactants by increasing the surfactant""s solubility in water and its stability in the formulation, especially in the presence of salts, electrolytes and/or pH agents.
These diols and alkoxylates correspond to structural formula (T)
HOxe2x80x94(Xxe2x80x94O)xRTxe2x80x94(Oxe2x80x94Y)yOHxe2x80x83xe2x80x83(T)
wherein each X and each Y is ethylene (that is, xe2x80x94C2H4xe2x80x94), propylene (that is, xe2x80x94C3H6xe2x80x94), or butylene (that is, xe2x80x94C4H8xe2x80x94); x is 0-40; y is 0-40; the sum (x+y) is 0-40; and RT is straight, branched or cyclic alkyl containing 4 to 12 carbon atoms. Preferably, RT contains 7-12 or even 7-9 carbon atoms.
The alkylene residue RT in structural formula (T) represents a saturated, straight-chain, branched-chain, or cyclic moiety containing 4 to 12 carbon atoms. It is preferred that RT is branched, wherein the term xe2x80x9cbranchedxe2x80x9d is intended to encompass structures having one side alkyl chain, more than one side alkyl chain, or one or more side alkyl chains, one or more of which is itself branched. Branched structures include cyclic structures substituted with one or more alkyl groups, the alkyl groups being straight or branched. Examples of suitable RT groups include such groups as xe2x80x94C(CH3)2CH2xe2x80x94,xe2x80x94CH2C(CH3)CH2xe2x80x94,xe2x80x94CH2CH2xe2x80x94,xe2x80x94CH2CH(CH3)2CH2xe2x80x94, xe2x80x94CH2CH(CH2CH3)CH2CH2CH2CH2xe2x80x94,xe2x80x94(CH2)6xe2x80x94,xe2x80x94CH2CH(CH2CH2CH2CH3)xe2x80x94, xe2x80x94CH2C(CH3)2CH(CH(CH3)2)xe2x80x94, and 
In the alkoxylated diols, the number of repeating units in each poly(alkoxy) chain can be up to 40, but it is preferred that each chain contains 1 to 10 repeating alkoxy units or more preferably 1 to 5 alkoxy units. The preferred alkoxy chains are poly(ethoxy), or are composed of 1 to 2 ethoxy units capped with a chain of 1 to 5 propoxy units.
Compounds of structural formula (T) defined above are in many instances commercially available. Compounds of structural formula (T) can be prepared in straightforward manner familiar to those of ordinary skill in this art by obtaining or preparing the corresponding precursor diol of structural formula HOxe2x80x94RTxe2x80x94OH, and then alkoxylating the precursor diol with a stoichiometrically appropriate number of moles of the desired corresponding alkylene oxide, such as ethylene oxide, propylene oxide, and/or butylene oxide. In those cases where it is desired to alkoxylate only one of the hydroxyl groups on the precursor diol, in some embodiments, the alkoxylation will preferentially occur at only one of the hydroxyl groups, particularly where one of hydroxyl groups is a primary hydroxyl and the other is a secondary hydroxyl. However, in those cases where both hydroxyl groups on the precursor diol might tend to alkoxylate, but alkoxylation at only one of the hydroxyl groups is desired, the hydroxyl group at which alkoxylation is desired not to occur can be protected by preliminarily reacting the hydroxyl group with a suitable protecting group such as a lower alkyl moiety or an esterifying substituent. Thereafter, following the alkoxylation, the protecting group is removed in a known manner.
Preferred examples of compounds of the foregoing structural formula (T) include any one, or mixtures, of 2,2,4-trimethyl-1,3-pentanediol (TMPD) and/or 2-ethylhexane-1,3-diol, and/or the reaction product of TMPD and/or 2-ethylhexane-1,3-diol with 1 to 10 moles of ethylene oxide, and preferably with 1 to 5 moles of ethylene oxide, as well as analogs alkoxylated with other C3 or C4 alkyl oxides or mixtures of any of C2, C3 and/or C4 alkyl oxides. Since the diol which is alkoxylated includes one primary hydroxyl group and one secondary hydroxyl group, the alkoxylation proceeds predominantly at the primary hydroxyl group.
The compositions which contain one or more Inventive Ester Quats can also contain one or a mixture of compounds of structural formula (E)
RE1xe2x80x94C(O)Oxe2x80x94RE2xe2x80x94OC(O)RE3)0-1xe2x80x83xe2x80x83(E)
wherein RE1 is straight, cyclic or branched alkyl containing 1-15 carbon atoms, and RE1 is substituted with 0 to 3 hydroxyl groups; and wherein RE2 is straight, cyclic or branched alkyl containing 1 to 10 carbon atoms, and RE2 is substituted with 0 to 3 hydroxyl groups, and RE2 can optionally be substituted with a group of the structure xe2x80x94OC(O)xe2x80x94RE3 wherein RE3 is straight, cyclic or branched alkyl containing 1 to 15 carbon atoms and is optionally substituted with a hydroxyl group.
Preferred compounds of structural formula (E) include those wherein RE2 contains 2 or 3 carbon atoms, for example, glycol and glyceryl derivative, or RE2 contains about 8 carbon atoms, for example, derivatives of 2,2,4-trimethylpentanediol or of 2-ethylhexanediol. Preferred compounds of structural formula (E) include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, hydroxypivalyl hydroxypivalate, and the monoester of TMPD with hydroxypivalic acid.
Formulations can also contain what may be termed aesthetic additives to provide properties such as fragrance, preservative, viscosity control, and color. Such additives are discussed below. The formulations according to the present invention generally exhibit highly satisfactory viscosities, generally as pourable and even sprayable fluids.
Other suitable non-quaternary compound surfactants, whether anionic, cationic, zwitterionic, nonionic, or amphoteric, may be used in combination with the compounds and formulations of the invention, depending on the application.
1. General Surfactants
For example, in a fabric softening application, suitable anionic surfactants may include, without limitation, the alkylbenzene sulfonates, xcex1-olefin sulfonates, and xylene sulfonates available from Witco Corporation under the WITCONATE(copyright) trademark. While these surfactants may be unsuitable for personal care applications because they may cause skin and eye irritation, surfactants suitable for personal care applications may be used in other non-personal care applications.
2. Personal Care Surfactants
For personal care applications, suitable anionic surfactants would include, without limitation, ammonium lauryl sulfate, sodium lauryl sulfate, any xcex1-olefin sulfonate, ammonium laureth sulfate (2 or 3 moles), sodium laureth sulfate (2 or 3 moles), sodium myristyl sulfate, sodium myristeth sulfate (1-4 moles), ammonium xylene sulfonate, sodium xylene sulfonate, TEA (triethanol amine) dodecylbenzene sulfonate, TEA lauryl sulfate, ammonium pareth sulfate, sodium pareth sulfate, sodium oleth sulfate, derivatives of any of the forgoing, and similar compounds known to those of skill in the art, and mixtures thereof. For personal care applications, suitable amphoteric surfactants or nonionic surfactants include betaines, sulfosuccinates, mono- and diglycerides, glycinates, sugars and derivatives thereof, hydroxysultaines, mono- and diacetates, ethoxylated derivatives of any of the forgoing, and similar compounds known to those of skill in the art, and mixtures thereof. Other surfactants that may be added to these systems include, but are not limited to, alkanolamides, come of which are available from Witco Corporation under the WITCAMDE(copyright) tradename. In addition, various amine oxides may be used in these systems, several of which are available from Witco Corporation under the VAROX(copyright) tradename.
Emollients and emulsifiers are also typically used in personal care formulations in combination with the amine compounds and quaternary compounds of the invention, depending on the application. Indeed, Inventive Ester Quats can be formulated into emulsions that can be used as skin or hair conditioners which can take the form of lotions, creams, leave-on products, and rinse-off products. These systems may also include additional products that may improve the feel and conditioning, or the emolliency of skin and hair. Some of these products are available from Witco Corporation under the KEMSTRENE(copyright), WITCONOL(trademark), STARFOL(copyright), and KEMESTER(copyright) tradenames. Although these emollients and emulsifiers are used in skin and hair conditioners, they can also be incorporated into other compositions containing Inventive Ester Quats for use in other products, such as tissues, that may contain a suitable lotion or cream therein.
A soft tissue that provides a soothing feel can be made by incorporating into the tissue a softening composition, whether or not aqueous, containing a combination of selected ingredients, including Inventive Ester Quats. Preferred tissues may include a softening composition comprising glycerin and one or more Inventive Ester Quats. The add-on amount of the softening composition can be any effective amount, the term xe2x80x9ceffective amountxe2x80x9d in this context meaning any amount that produces the benefits of the softening composition desired, for example, providing a softening or moisturizing effect on skin brought into contact with tissues containing the softening composition. In general, the amount of softening composition will be about 3 wt. % to about 30 wt. %, more preferably about 3 wt. % to about 20 wt. %, and still more preferably about 5 wt. % to about 15 wt. %, based on the weight of the untreated tissue. The higher add-on amounts are more likely to leave behind a detectable residue on the skin, whereas the lower add-on amounts are less likely to do so. As would be understood by those of skill in the art, water can be added to the formulation to reduce the viscosity of the glycerin and to make the formulation more suitable for application. The amount of Inventive Ester Quat in the softening composition is generally from about 0.2 wt. % to about 5 wt. %, more preferably from about 0.3 wt. % to about 3 wt. %. and most preferably from about 0.5 wt. % to about 1 wt. % of the softening composition. The amount of glycerin, diol, glycol, or similar additive or mixture thereof in the softening composition can be from about 20 wt. % to about 98 wt. %, preferably from about 60 wt. % to about 80 wt. %, and most preferably from about 40 wt. % to about 60 wt. % of the softening composition. Other optional ingredients include aloe, humectants, skin protectants, preservatives, and feel modifiers. The softening composition, which can be in the form of a solution or suspension, can be incorporated into the tissue by any suitable means such as spraying or printing onto the surface of the tissue. The tissue to which the softening composition is applied can be any tissue useful as facial tissue, bath tissue, or towels, and such tissues can be produced by throughdrying or wet-pressing tissue making processes and can be creped or uncreped, layered or non-layered (blended).
Other additives and adjuvants can be optionally added to the compounds and formulations of the present invention for their known purposes. Such additives and adjuvants include, but are not limited to, perfumes, preservatives including bacteriocides and fungicides, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, especially bluing agents, viscosity control agents, antioxidants, silicones, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, aloe, humectants, skin protectants, feel modifiers, waxes, glycerin, vitamins and extracts, and mixtures thereof. The identity and amounts of the additives and adjuvants used would depend on the application of the formulation and its desired properties; many of the additives set forth below are not exclusive to any one formulation or application, but may be appropriate for many different formulations or applications. The additives and adjuvants are well-known to those of skill in the art and the additives and adjuvants listed below are not meant to be an exhaustive list but merely a guide to the types of additives that would typically be used.
1. Papermaking and Tissuemaking Additives
Paper and tissue softening or debonding compositions of the present invention would typically contain other chemicals commonly used in papermaking or tissuemaking, or to the paper or tissue furnish so long as they do not significantly and adversely affect the softening, absorbency of the fibrous material, and softness enhancing actions of the amine and quaternary ammonium softening compounds of the present invention.
A. Wetting Agents
The present invention may contain as an optional ingredient from about 0.005% to about 3.0%, more preferably from about 0.03% to 1.0% by weight, on a dry fiber basis of a wetting agent. Such wetting agents may be selected from polyhydroxy compounds, nonionic surfactants such as alkoxylated compounds and linear alkoxylated alcohols, and anionic wetting agents such as diisooctylsulfosuccinate (DOSS), available from Witco Corporation under the tradename EMCOL(copyright) 4500.
Examples of water soluble polyhydroxy compounds that can be used as wetting agents in the present invention include glycerol, polyglycerols having a weight-average molecular weight of from about 150 to about 800, and polyoxyethylene glycols and polyoxypropylene glycols having a weight-average molecular weight of from about 200 to about 4000, preferably from about 200 to about 1000, most preferably from about 200 to about 600. Polyoxyethylene glycols having an weight-average molecular weight of from about 200 to about 600 are especially preferred. Mixtures of the above-described polyhydroxy compounds may also be used. A particularly preferred polyhydroxy compound is polyoxyethylene glycol having an weight average molecular weight of about 400, available from Union Carbide Corporation under the tradename PEG-400.
Suitable nonionic surfactants can be used as wetting agents in the present invention. These include addition products of alkoxylating agents such as ethylene oxide (EO), propylene oxide (PO), or butylene oxide (BO), or a mixture thereof, with fatty alcohols, fatty acids, fatty amines, etc. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant. Suitable compounds are substantially water-soluble surfactants of the general formula:
R10xe2x80x94Yxe2x80x94(C2H4O)zxe2x80x94C2H4OH
wherein R10 for both solid and liquid compositions is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a hydrocarbyl chain length of from about 8 to about 20, preferably from about 10 to about 18 carbon atoms. More preferably the hydrocarbyl chain length for liquid compositions is from about 16 to about 18 carbon atoms and for solid compositions from about 10 to about 14 carbon atoms. In the general formula for the ethoxylated nonionic surfactants herein, Y is typically xe2x80x94Oxe2x80x94, xe2x80x94C(O)Oxe2x80x94, xe2x80x94C(O)N(R11)xe2x80x94, or xe2x80x94C(O)N(R11)R11xe2x80x94, in which R10, and R11, when present, have the meanings given hereinbefore, and/or R11 can be hydrogen, and z is at least about 8, preferably at least about 10-11. Performance and, usually, stability of the softener composition decrease when fewer ethoxylate groups are present.
Examples of nonionic surfactants according to the above formula follow, wherein the integer in parenthesis identifies the number of EO groups in the molecule. In particular, the deco-, under-, dodder-, terraced-, and pentadecaethoxylates of n-hexadecanol and n-octadecanol are useful wetting agents in the context of this invention. Exemplary ethoxylated primary alcohols useful herein as the viscosity/dispersibility modifiers of the compositions are n-octadecanol EO(10); and n-decanol EO(11). The ethoxylates of mixed natural or synthetic alcohols in the xe2x80x9coleylxe2x80x9d chain length range are also useful herein. Specific examples of such materials include oleyl alcohol EO(11), oleyl alcohol EO(18), and oleyl alcohol EO(25). In addition, the deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, and nonadecaethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol can be used as wetting agents in the present invention.
As in the case of the alcohol alkoxylates, the hexa- through octadecaethoxylates of alkylated phenols, particularly monohydric alkylphenols, are useful as the viscosity/dispersibility modifiers of the instant compositions. In particular, the hexa- through octadeca-ethoxylates of p-tridecylphenol, m-pentadecylphenol, and the like, are useful herein. Exemplary ethoxylated alkylphenols useful as the wetting agents of the mixtures herein are: p-tridecylphenol EO(11) and p-pentadecylphenol EO(18). As used herein and as generally recognized in the art, a phenylene group in the nonionic formula is the equivalent of an alkylene group containing from 2 to 4 carbon atoms. It should also be noted that the alkenyl alcohols, both primary and secondary, and alkenyl phenols corresponding to those disclosed immediately hereinabove can be ethoxylated and used as wetting agents in the present invention. Furthermore, branched-chain primary and secondary alcohols, usually synthesized using the well-known Oxo Process, can be ethoxylated and can be used as wetting agents in the present invention.
The above ethoxylated nonionic surfactants are useful in the present compositions alone or in combination, and the term xe2x80x9cnonionic surfactantxe2x80x9d encompasses mixed nonionic surface active agents. The level of surfactant, if used, is preferably from about 0.01% to about 2.0% by weight, based on the dry fiber weight of the tissue paper. The surfactants preferably have alkyl chains with eight or more carbon atoms. Exemplary anionic surfactants are linear alkyl sulfonates, and alkylbenzene sulfonates. Exemplary nonionic surfactants are alkylglycosides including alkylglycoside esters such as that available from Croda, Inc. under the tradename CRODESTA(trademark) SL40; alkylglycoside ethers as described in U.S. Pat. No. 4,011,389, which patent is herein incorporated by reference in its entirety; and alkylpolyethoxylated esters such as those available from Lonza Inc. under the tradename PEGOSPERSE(copyright) 200 ML and available from Rhxc3x4ne-Poulenc Corporation under the tradename IGEPAL(copyright) RC-520.
B. Strength Additives
Other types of chemicals which may be added, include the strength additives to increase the dry tensile strength and the wet burst of the tissue webs. The present invention may contain as an optional component from about 0.01 wt. % to about 3.0 wt. %, more preferably from about 0.3 wt. % to about 1.5 wt. %, on a dry fiber weight basis, of a water-soluble strength additive resin. Such water-soluble strength additive resins may include dry strength additives, permanent wet strength resins, temporary wet strength resins, or a compatible mixture thereof.
Examples of suitable dry strength additives include carboxymethyl cellulose and cationic polymers from the ACCO chemical family such as ACCO 711 and ACCO 514, with ACCO chemical family being preferred. These materials are available commercially from the American Cyanamid Company.
As used herein, the term xe2x80x9cpermanent wet strength resinxe2x80x9d refers to a resin which allows the paper sheet, when placed in an aqueous medium, to keep a majority of its initial wet strength for a period of time greater than at least two minutes. Permanent wet strength resins useful herein can be of several types. Generally, those resins which have previously found and which will hereafter find utility in the papermaking art are useful herein. Numerous examples are described by Westfelt in Cellulose Chemistry and Technology, Volume 13, at pages 813-825 (1979), which is herein incorporated by reference in its entirety. Usually, the wet strength resins are water-soluble, cationic materials. That is to say, the resins are water-soluble at the time they are added to the papermaking furnish. It is quite possible, and even to be expected, that subsequent events such as cross-linking will render the resins insoluble in water. Further, some resins are soluble only under specific conditions, such as over a limited pH range. Wet strength resins are generally believed to undergo a cross-linking or other curing reactions after they have been deposited on, within, or among the papermaking fibers. However, such cross-linking or curing does not normally occur so long as substantial amounts of water are present.
Of particular utility are the various polyamide-epichlorohydrin resins. These materials are low molecular weight polymers provided with reactive functional groups such as amino, epoxy, and azetidinium groups. The patent literature is replete with descriptions of processes for making such materials, for example, U.S. Pat. Nos. 3,700,623 and 3,772,076, both herein incorporated by reference in their entireties. Such polyamide-epichlorohydrin resins available from Hercules Inc. under the trademarks KYMENE(copyright) 557H and KYMENE(copyright) 2064 are particularly useful in this invention. In addition, base-activated polyamide-epichlorohydrin resins are generally described in U.S. Pat. Nos. 3,855,158; 3,899,388; 4,129,528; 4,147,586; and 4,222,921, which patents are herein incorporated by reference in their entireties. These materials are available from the Monsanto Company under the tradename SANTO-REST(trademark), such as SANTO-REST(trademark) 31.
Other water-soluble cationic resins useful herein are the polyacrylamide resins, such as those generally described in U.S. Pat. Nos. 3,556,932 and 3,556,933, which are both herein incorporated by reference in their entireties. Such materials are available from the American Cyanamid Company under the tradename PAREZ(copyright), such as PAREZ(copyright) 631NC. Other types of water-soluble resins useful in the present invention include acrylic emulsions and anionic styrene-butadiene latexes, numerous examples of which are provided in U.S. Pat. No. 3,844,880, which is herein incorporated by reference in its entirety. Still other water-soluble cationic resins finding utility in this invention are the urea formaldehyde and melamine formaldehyde resins. These polyfunctional, reactive polymers have molecular weights on the order of a few thousand. The more common functional groups include nitrogen containing groups such as amino groups and methylol groups attached to nitrogen. Although less preferred, polyethylenimine-type resins find utility in the present invention. More complete descriptions of the aforementioned water-soluble resins, including their manufacture, can be found in TAPPI Monograph Series No. 29, Wet Strength In Paper and Paperboard, Technical Association of the Pulp and Paper Industry (New York: 1965), which is herein incorporated by reference in its entirety.
The above-mentioned permanent wet strength additives are those that produce paper products with permanent wet strength, that is, paper which when placed in an aqueous medium retains a substantial portion of its initial wet strength over time. However, permanent wet strength in some types of paper products can be an unnecessary and undesirable property. Paper products such as toilet tissues, etc., are generally disposed of after brief periods of use into septic systems and the like. Clogging of these systems can result if the paper product permanently retains its hydrolysis-resistant strength properties. Thus, manufacturers use temporary wet strength additives to paper products for which wet strength is sufficient for the intended use, but which then decays upon soaking in water. Decay of the wet strength facilitates flow of the paper product through septic systems.
Examples of suitable temporary wet strength resins include modified starch temporary wet strength agents, such as that available from the National Starch and Chemical Corporation under the tradename NATIONAL STARCH(trademark) 78-0080. This type of wet strength agent can be made by reacting dimethoxyethyl-N-methyl-chloroacetamide with cationic starch polymers. Modified starch temporary wet strength agents are also described in U.S. Pat. Nos. 4,675,394 and 4,981,557, both of which are herein incorporated by reference in their entireties.
C. Other Additives
Other suitable additives may be used in paper and tissuemaking applications, depending on the application. For example, glycerin may also be used in the composition and formulations thereof. If used, the amount of glycerin in the aqueous softening composition can be from about 0.1 wt. % to about 98 wt. %, more preferably from about 60 to about 80 wt. %, and still more preferably from about 40 to about 60 wt. %, of the composition. In addition, the compositions and formulations of the instant invention can contain glycols, such as propylene glycol or polyethylene glycol, or mineral oils instead of, or, in addition, to glycerin in such formulations. Silicones and other additives set forth below may also be used in combination with Inventive Ester Quats, either together or sequentially in the papermaking or tissuemaking process, for example, when Inventive Ester Quats are applied to the wet end and a silicone is topically applied by print or spray or, alternatively, the Inventive Ester Quat and silicone are both used in the wet end or are both sprayed topically on the furnish.
2. Perfumes
As noted above, perfumes or fragrance materials may be added to the compositions and formulations of the present invention. The selection of the perfume or perfumes is based upon the application, the desired effect on the consumer, and preferences of the formulator. The perfume selected for use in the compositions and formulations of the present invention contains ingredients with odor characteristics which are preferred in order to provide a fresh impression on the surface to which the composition is directed, for example, those which provide a fresh impression for fabrics if a fabric softener treatment formulation is prepared. Such perfume is preferably present at a level of from about 0.01% to about 5%, preferably from about 0.05% to about 3%, more preferably from about 0.1% to about 2%, by weight of the total composition.
Preferably, the perfume is composed of fragrance materials selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240 m: aliphatic ketones having molecular weights from about 150 to about 260; aromatic ketones having molecular weights from about 150 to about 270; aromatic and aliphatic lactones having molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having molecular weights from about 150 to about 270; and condensation products of aldehydes and amines having molecular weights from about 180 to about 320; and mixtures thereof.
The selection of such perfumes and fragrance materials are well-known to those of skill in the art, both for desired scent and appropriate scent impact. For example, when high initial perfume odor impact on fabrics is desired, it is preferable to select a perfume containing perfume ingredients which are not too hydrophobic. The degree of hydrophobicity of a perfume ingredient can be correlated with its octanol/water partitioning coefficient P, the ratio between its equilibrium concentration in octanol and in water. Thus, a perfume ingredient with a greater partitioning coefficient P is more hydrophobic and a perfume ingredient with a smaller partitioning coefficient P is more hydrophilic; a selection based on the application and intended effect may be made accordingly. For example, in a fabric application, the preferred perfume ingredients would have an octanol/water partitioning coefficient P of about 1,000 or smaller.
3. Preservatives
Optionally, solubilized, water-soluble preservatives can be added to the present invention. Preservatives are especially preferred when organic compounds that are subject to microorganisms are added to the compositions of the present invention, especially when they are used in aqueous compositions. When such compounds are present, long term and even short term storage stability of the compositions and formulations becomes an important issue since contamination by certain microorganisms with subsequent microbial growth often results in an unsightly and/or malodorous solution. Therefore, because microbial growth in these compositions and formulations is highly objectionable when it occurs, it is preferable to include a solubilized water-soluble, antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear and often aqueous compositions and formulations of the present invention.
Typical microorganisms that can be found in personal care products include bacteria, for example, Bacillus thuringiensis (cereus group) and Bacillus sphaericus, and fungi, for example, Aspergillus ustus. Bacillus sphaericus is one of the most numerous members of Bacillus species in soils. In addition, microorganisms such as Escherichia coli and Pseudomonas aerupinosa are found in some water sources, and can be introduced during the preparation of aqueous solutions of the present invention.
It is preferable to use a broad spectrum preservative, for example, one that is effective on both bacteria (both gram positive and gram negative) and fungi. A limited spectrum preservative, for example, one that is only effective on a single group of microorganisms, for example, fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity. A mixture of broad spectrum preservatives can also be used.
Antimicrobial preservatives useful in the present invention can be biocidal compounds, that is, substances that kill microorganisms, or biostatic compounds, that is, substances that inhibit and/or regulate the growth of microorganisms. Preferred antimicrobial preservatives are those that are water-soluble and are effective at low levels. In general, the water-soluble preservatives that may be used include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof. Examples of preservatives useful in the present invention include, but are not limited to, the short chain alkyl esters of p-hydroxybenzoic acid (commonly known as parabens); N-(4-chlorophenyl)-N-(3,4-dichlorophenyl) urea (also known as 3,4,4xe2x80x2-trichlorocarbanilide or triclocarban); 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenyl ether, commonly known as triclosan); the isothiazoline formulation available from Sterling-Winthrop Group Ltd. under the tradename PARMETOL(trademark) K-40; a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available from the Rohm and Haas Company as a 1.5% aqueous solution under the tradename KATHON(copyright) CG; 5-bromo-5-nitro-1,3-dioxane, available from Henkel Corporation under the tradename BRONIDOX(copyright) L; 2-bromo-2-nitropropane-1,3-diol, available from Inolex Chemical Company under the tradename BRONOPOL(trademark); 1,1xe2x80x2-hexamethylenebis(5-(p-chlorophenyl)biguanide) (commonly known as chlorhexidine) and its salts, for example, with acetic and digluconic acids; a 95:5 mixture of 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and 3-butyl-2-iodopropynyl carbamate, available from Lonza Inc. under the tradename GLYDANT(copyright) Plus; N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,Nxe2x80x2-bis(hydroxy-methyl) urea, commonly known as diazolidinyl urea, available from Sutton Laboratories, Inc. under the tradename GERMALL(copyright) II; N,Nxe2x80x3-methylenebis[Nxe2x80x2-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea] (commonly known as imidazolidinyl urea), available, for example, from 3V-Sigma under the tradename ABIOL(trademark), from Induchem under the tradename UNICIDE(copyright) U-13, and from Sutton Laboratories, Inc. under the tradename GERMALL(copyright) 115; polymethoxy bicyclic oxazolidine, available from Hxc3xcls America Inc. under the tradename NUOSEPT(copyright); formaldehyde; glutaraldehyde; polyaminopropyl biguanide, available from ICI Americas, Inc. under the tradename COSMOCIL(copyright) CQ or from Brooks Industries Inc. under the tradename MIKROKILL(trademark); dehydroacetic acid; and mixtures thereof. In general, however, the preservative can be any organic preservative material which is appropriate for the application, for example, in a fabric softening application such preservative will preferably not cause damage to fabric appearance, for example, discoloration, coloration, or bleaching of the fabric.
If the antimicrobial preservative is included in the compositions and formulations of the present invention, it is preferably present in an effective amount, wherein an xe2x80x9ceffective amountxe2x80x9d means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time. Preferred levels of preservative are from about 0.0001% to about 0.5%, more preferably from about 0.0002% to about 0.2%, most preferably from about 0.0003% to about 0.1%, by weight of the composition.
Bacteriostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, for example, less than about pH 4, preferably less than about pH 3. Low pH for microbial control is not a preferred approach in the present invention because the low pH can cause chemical degradation of the cyclodextrins. Therefore, aqueous compositions of the present invention should have a pH greater than about 3.0, preferably greater than about 4.0, more preferably greater than about 4.5. As stated above, it is preferable to use the preservative at an effective amount, as defined hereinabove. Optionally, however, the preservative can be used at a level which provides an antimicrobial effect on the treated fabrics.
4. Antistatic Agents
The composition of the present invention can optionally contain an effective amount of antistatic agent to provide the treated clothes with in-wear static. Preferred antistatic agents are those that are water soluble in at least effective amount, such that the composition remains a clear solution. Examples of these antistatic agents include monoalkyl cationic quaternary ammonium compounds, for example, mono(C10-C14 alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride (available from Henkel Corporation under the tradename DEHYQUART(copyright) E), and ethyl bis(polyethoxyethanol) alkylammonium ethylsulfate (available from Witco Corporation under the tradename VARIQUAT(copyright) 66), polyethylene glycols, polymeric quaternary ammonium salts (such as those available from Rhxc3x4ne-Poulenc Corporation under the MRAPOL(copyright) tradename), quaternized polyethyleneimines, vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer (available from GAF Corporation under the tradename GAFQUAT(copyright) HS-100), triethonium hydrolyzed collagen ethosulfate (available from Maybrook Inc. under the tradename QUAT-PRO(trademark) E), and mixtures thereof. When an antistatic agent is used it is typically present at a level of from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.3% to about 3%, by weight of the composition.
5. Defoaming and Antifoaming Agents
In many applications, it is preferred that a defoaming or antifoaming agent is used, to avoid foam formation during application and use of the Inventive Ester Quats. Typical defoaming or antifoaming agents include various alcohols, hydrocarbons, silicones, alcohol alkoxylates, propoxylated alkyl amines, polyacrylates, alkyleneoxide copolymers, fatty acids, fatty acid sulfonates and blends of fatty acids and esters in hydrocarbons. It is also preferred that polyethoxylated agents such as polyethylene glycol or VARIQUAT(copyright) 66 are not used when xcex1-cyclodextrin is used.
6. Enzymes
In another useful aspect of the present invention, the compositions can also contain an effective amount of an enzyme component which comprises one or more enzymes capable of assisting the removal of stain or soil from a surface. The enzyme component includes any enzyme which assists in the removal of soil or stain from a substrate (including particularly fabric and hard surfaces). Particularly useful enzymes include carbohydrases, especially amylases, xcex1-amylases, and xcex2-amylases, and cellulases; lipases; and proteases. Amylases and cellulases are particularly useful against carbohydrates, for example. starches and other polysaccharides. Thus amylases and cellulases provide cleaning activity against plant-derived soil and stains, such as grass stains, coffee, tea, grape juice, ketchup, and the like. Lipases are esterases which hydrolyze esters of glycerol and fatty acids. Thus, lipases are particularly useful in providing cleaning activity against soil and stains which contain an ester linkage, such as oils, fats, and greases. Proteases hydrolyze peptides and proteins, and thus are particularly useful in providing cleaning activity against proteinaceous soil and stains such as blood as well as other foreign materials containing an amide bond.
A preferred xcex1-amylase is Termamyl, which is derived from B. licheniformis. Other useful xcex1-amylases include Alphamyl, Asperzyme, Clarase, Mycolase, Mycozyme, Rapidase, Rhozyme, and Tenase. A preferred cellulase is Celluzyme. A preferred lipase is Lipolase. Other useful lipases include pancreatin. A preferred protease is Alcalase. Other preferred proteases include Esperase. The enzyme component generally comprises 0.1 wt. % up to about 5 wt. % and preferably 0.5 wt. % to 2 wt. %, by weight of the total composition.
7. Dyes and Colorants
Colorants and dyes, especially bluing agents, can be optionally added to the compositions of the present invention for visual appeal and performance impression. When colorants are used, they are used at extremely low levels to avoid fabric staining. Preferred colorants for use in the present compositions are highly water-soluble dyes, for example, LIQUITINT(copyright) dyes available from Milliken Chemical Company. Any dye can be used in the compositions of the present invention, but nonionic dyes are preferred to decrease interaction with dye transfer inhibitor. For many personal care products using the present invention, colorants are also added at extremely low levels. Color additives for products to be marketed in the United States are named in compliance with Title 21 of the U.S. Code of Federal Regulations.
8. Insect and Moth Repelling Agents
The composition of the present invention can optionally contain an effective amount of insect or moth repelling agents. Typical insect and moth repelling agents are pheromones, such as anti-aggregation pheromones, and other natural and/or synthetic ingredients. Preferred insect and moth repellent agents useful in the composition of the present invention are perfume ingredients, such as citronellol, citranellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 2-(diethylphenoxy)ethanol, 1-dodecene, and the like. Other examples of insect and/or moth repellents useful in the composition of the present invention are disclosed in U.S. Pat. Nos. 4,449,987; 4,693,890; 4,696,676; 4,933,371; 5,030,660; and 5,196,200; and in B. D. Mookherjee et al., xe2x80x9cSemio Activity of Flavor and Fragrance Molecules on Various Insect Speciesxe2x80x9d, published in Bioactive Volatile Compounds from Plants, ASC Symposium Series 525, R. Teranishi, R. G. Buttery, and H. Sugisawa (eds.), 1993, pp. 35-48. All of these patents and publications are herein incorporated by reference in their entireties. When an insect and/or moth repellent is used it is typically present at a level of from about 0.005 wt. % to about 3 wt. % of the composition.
9. Polymeric Soil Release Agents
Soil release agents, usually polymers, are especially desirable additives at levels of from about 0.05 wt. % to about 5 wt. %, preferably from about 0.1 wt. % to about 4 wt. %, more preferably from about 0.2 wt. % to about 3 wt. %. Suitable soil release agents are disclosed in U.S. Pat. Nos. 4,702,857; 4,711,730; 4,713,194; 4,877,896; 4,956,447; and 4,749,596, all of these patents being herein incorporated by reference in their entireties.
Especially desirable optional ingredients are polymeric soil release agents comprising block copolymers of polyalkylene terephthalate and polyoxyethylene terephthalate, and block copolymers of polyalkylene terephthalate and polyethylene glycol. The polyalkylene terephthalate blocks preferably comprise ethylene and/or propylene groups. Many such soil release polymers are nonionic, for example, the nonionic soil release polymer is described in U.S. Pat. No. 4,849,257, which patent is herein incorporated by reference in its entirety.
The polymeric soil release agents useful in the present invention can include anionic and cationic polymeric soil release agents. Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Pat. No. 4,018,569, which patent is herein incorporated by reference in its entirety. Other suitable polymers are disclosed in U.S. Pat. No. 4,808,086, which patent is herein incorporated by reference in its entirety. Suitable cationic soil release polymers are described in U.S. Pat. No. 4,956,447, which patent has already been herein incorporated by reference.
10. Viscosity Control Agents
Viscosity control agents can be organic or inorganic in nature and may either lower or raise the viscosity of the formulation. Examples of organic viscosity modifiers (lowering) are aryl carboxylates and sulfonates (for example, benzoate, 2-hydroxybenzoate, 2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, and the like), fatty acids and esters, fatty alcohols, and water-miscible solvents such as short chain alcohols. Examples of inorganic viscosity control agents are water-soluble ionizable salts. A wide variety of ionizable salts can be used. Examples of suitable salts are the halides and acetates of ammonium ion and the group IA and IIA metals of the Periodic Table of the Elements, for example, calcium chloride, lithium chloride. sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, ammonium iodide, sodium acetate, potassium acetate, or mixtures thereof. Calcium chloride is preferred. The ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity. The amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desire of the formulator. Typical levels of salts used to control the composition viscosity are from 0 to about 10 wt. %, preferably from about 0.01 wt. % to about 6 wt. %, and most preferably from about 0.02 wt. % to about 3 wt. % of the composition.
Viscosity modifiers (raising) or thickening agents can be added to increase the ability of the compositions to stably suspend water-insoluble articles, for example, perfume microcapsules. Such materials include hydroxypropyl substituted guar gum (such as that available from Rhxc3x4ne-Poulenc Corporation under the tradename JAGUAR(copyright) HP200), polyethylene gycol (such as that available from Union Carbide Corporation under the tradename CARBOWAX(copyright) 20M), hydrophobic modified hydroxyethylcellulose (such as that available from the Aqualon Company under the tradename NATROSOL(copyright) Plus), and/or organophilic clays. These viscosity raisers (thickeners) are typically used at levels from about 0.5 wt. % to about 30 wt. %, preferably from about 1 wt. % to about 5 wt. %, more preferably from about 1.5 wt. % to about 3.5 wt. %, and most preferably from about 2 wt. % to about 3 wt. %, of the composition.
11. Pearlizing and Opacifying Agents
Examples of pearlizing or opacifying agents that can be added to the compositions of this invention include, but are not restricted to, glycol distearate, propylene glycol distearate, and glycol stearate. Some of these products are available from Witco Corporation under the KEMESTER(copyright) tradename.
12. Vitamins and Extracts
In personal care applications, vitamins and extracts are often used in the formulations thereof. Examples of vitamins that can be added to the compositions of this invention include, but are not restricted to, vitamins A1, A2, B1, B2, B6, B12, C, D, E, H, and K, the provitamins, salts, derivatives, and complexes thereof, and mixtures thereof. Examples of extracts that can be added to the compositions of this invention include, but are not restricted to, rosemary extract, carrot extract, Camelina sativa, camomile extract, egg yolk extract, elm extract, acacia extract, rose extract, lilac extract, licorice extract, lemon extract, orange extract, lime extract, linden extract, melon extract, peach extract, orchid extract, orris extract, and the like, and mixtures thereof.
13. Antioxidants
Examples of antioxidants that can be added to the compositions of this invention are propyl gallate, available from Eastman Chemical Products, Inc. under the tradenames TENOX(copyright) PG and TENOX(copyright) S-1, and dibutylated hydroxytoluene, available from UOP Inc. under the tradename SUSTANE(copyright) BHT.
14. Silicones
The present compositions can contain silicones to provide additional benefits, for example, in a fabric application they may provide ease of ironing and improved fabric absorbency. As used herein, the term xe2x80x9csiliconesxe2x80x9d comprises cationic and amphoteric silicones, polysiloxanes, and polysiloxanes having hydrogen-bonding functional groups consisting of amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups. Such polysiloxanes include, but are not limited to, polyether-modified polysiloxanes, amino-modified polysiloxanes, epoxy-modified polysiloxanes, polyhydrido-modified polysiloxanes, phenol-derivative-modified polysiloxanes, ABA-type polysiloxanes,[AB]N-type polysiloxanes, amino[AB]N-type polysiloxanes, including those available from OSi Specialties, Inc. (a division of Witco Corporation), under the SILWET(copyright), NUWET(copyright), NUDRY(trademark), NUSOFT(trademark), MAGNASOFT(copyright) tradenames.
Suitable silicones may include polydimethylsiloxanes of viscosity of from about 100 centistokes (cs) to about 100,000 cs, preferably from about 200 cs to about 60,000 cs and/or silicone gums. These silicones can be used in emulsified form, which can be conveniently obtained directly from the suppliers. Examples of these preemulsified silicones are the 60% emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning Corporation under the tradename DOW CORNING(copyright) 1157 Fluid and the 50% emulsion of polydimethylsiloxane (10,000 cs) sold by General Electric Company under the tradename GENERAL ELECTRIC(copyright) SM 2140 silicones. The optional silicone component can be used in an amount of from about 0.1 wt. % to about 6 wt. % of the composition.
Silicone foam suppressants can also be used. These are usually not emulsified and typically have viscosities of from about 100 cs to about 10,000 cs, preferably from about 200 cs to about 5,000 cs. Very low levels are used, typically from about 0.01% to about 1%, preferably from about 0.02% to about 0.5%. Another preferred foam suppressant is a silicone/silicate mixture, for example, Dow Corning""s ANTIFOAM(trademark) A.
15. Lubrication and Slip Additives
Compositions and formulations of the present invention can contain additives such as water, insoluble organics such as fatty acids, fatty esters, triglycerides, oils, alcohols, fatty alcohols, fatty amines and derivatives, amides, hydrocarbons, mineral oils, waxes, and the like, and mixtures thereof, as lubrication and slip agents.
16. Dye Transfer Inhibitors
Compositions and formulations of the present invention can contain ethoxylated amines, amphoterics, betaines, sulfosuccinates, sulfobetaines, polymers such as polyvinylpyrrolidone, and other ingredients that inhibit dye transfer.
Other optional ingredients include aloe, humectants, skin protectants, and feel modifiers. Suitable humectants include lactic acid and its salts, sugars, ethoxylated glycerin. ethoxylated lanolin, corn syrup, hydrolyzed starch hydrolysate, urea, and sorbitol. Suitable skin protectants include allantoin, kaolin, and zinc oxide. Suitable feel modifiers include corn starch, oat flour, talc, boron nitride, and cyclodextrin.